Thermoplastic polymer composition

ABSTRACT

The invention provides a compound conforming to the structure of Formula (CX) 
     
       
         
         
             
             
         
       
     
     The invention also provides a thermoplastic polymer composition comprising a polyolefin polymer and a compound conforming to the structure of Formula (CX) as a nucleating agent.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims, pursuant to 35 U.S.C. §119(e)(1), priority toand the benefit of the filing date of U.S. Patent Application No.61/881,227 filed on Sep. 23, 2013, which application is herebyincorporated by reference in its entirety.

TECHNICAL FIELD OF THE INVENTION

This application relates to nucleating agents for thermoplasticpolymers, thermoplastic polymer compositions comprising such nucleatingagents, articles made from such thermoplastic polymer compositions, andmethods for making and molding such thermoplastic polymer compositions.

BACKGROUND

Several nucleating agents for thermoplastic polymers are known in theart. These nucleating agents generally function by forming nuclei orproviding sites for the formation and/or growth of crystals in thethermoplastic polymer as it solidifies from a molten state. The nucleior sites provided by the nucleating agent allow the crystals to formwithin the cooling polymer at a higher temperature and/or at a morerapid rate than the crystals will form in the virgin, non-nucleatedthermoplastic polymer. These effects can then permit processing of anucleated thermoplastic polymer composition at cycle times that areshorter than the virgin, non-nucleated thermoplastic polymer.

While polymer nucleating agents may function in a similar manner, notall nucleating agents are created equal. For example, a particularnucleating agent may be very effective at increasing the peak polymerrecrystallization temperature of a thermoplastic polymer, but the rapidrate of crystallization induced by such a nucleating agent may causeinconsistent shrinkage of a molded part produced from a thermoplasticpolymer composition containing the nucleating agent. Such a nucleatingagent may also be ineffective in increasing the stiffness of the moldedpart to a desirable degree. Also, while nucleating agents forpolyethylene polymers are known in the art, relatively few of thesenucleating agents have been shown to improve the physical properties ofthe polyethylene polymer to any commercially significant degree.

Given the complicated interrelationship of these properties and the factthat many nucleating agents exhibit less-than-optimal behavior in atleast one respect, a need remains for nucleating agents that are capableof producing thermoplastic polymer compositions exhibiting a moredesirable combination of high peak polymer recrystallizationtemperature, tunable shrinkage, and high stiffness. Applicants believethat the nucleating agents and thermoplastic polymer compositionsdisclosed in the present application meet such a need.

BRIEF SUMMARY OF THE INVENTION

As noted above, the present application generally relates to nucleatingagents, thermoplastic polymer compositions comprising such nucleatingagents, articles (e.g., molded articles) made from such thermoplasticpolymer compositions, and methods for making and molding suchthermoplastic polymer compositions. The nucleating agents andthermoplastic polymer compositions according to the invention arebelieved to be particularly well-suited for the production ofthermoplastic polymer articles (e.g., molded thermoplastic polymerarticles) exhibiting a desirable combination of physical properties. Inparticular, articles produced using the nucleating agents andthermoplastic polymer compositions of the invention are believed toexhibit a desirable combination of a higher peak polymerrecrystallization temperature and improved physical properties (e.g.,tear strength) as compared to articles made from the non-nucleatedthermoplastic polymer. Applicants believe that this combination ofphysical properties indicates that the nucleating agents andthermoplastic polymer compositions according to the invention arewell-suited for use in the production of thermoplastic polymer articles.

In a first embodiment, the invention provides a thermoplastic polymercomposition comprising:

(a) a polyolefin polymer; and

(b) a nucleating agent, the nucleating agent comprising a compoundconforming to the structure of Formula (I)

wherein R₁ is selected from the group consisting of hydroxy, halogens,alkyl groups, substituted alkyl groups, alkoxy groups, substitutedalkoxy groups, aryl groups, and substituted aryl groups; n is zero or apositive integer from 1 to 4; L is a linking group comprising two ormore atoms and at least one double bond between two atoms in the linkinggroup; v is a positive integer from 1 to 3; R₂ is: (i) selected from thegroup consisting of alkyl groups, substituted alkyl groups, cycloalkylgroups, substituted cycloalkyl groups, aryl groups, substituted arylgroups, heteroaryl groups, and substituted heteroaryl groups when L is adivalent linking group and v is 1, (ii) selected from the groupconsisting of alkanediyl groups, substituted alkanediyl groups,cycloalkanediyl groups, substituted cycloalkanediyl groups, arenediylgroups, substituted arenediyl groups, heteroarenediyl groups, andsubstituted heteroarenediyl groups when L is a trivalent linking groupand v is 1, (iii) selected from the group consisting of alkanediylgroups, substituted alkanediyl groups, cycloalkanediyl groups,substituted cycloalkanediyl groups, arenediyl groups, substitutedarenediyl groups, heteroarenediyl groups, and substitutedheteroarenediyl groups when L is a divalent linking group and v is 2,and (iv) selected from the group consisting of alkanetriyl groups,substituted alkanetriyl groups, cycloalkanetriyl groups, substitutedcycloalkanetriyl groups, arenetriyl groups, substituted arenetriylgroups, heteroarenetriyl groups, and substituted heteroarenetriyl groupswhen L is a divalent linking group and v is 3; x is a positive integer;each M₁ is a metal cation; y is the valence of the cation; z is apositive integer; b is zero or a positive integer; when b is a positiveinteger, each Q₁ is a negatively-charged counterion and a is the valenceof the negatively-charged counterion; and the values of v, x, y, z, a,and b satisfy the equation (vx)+(ab)=yz; wherein the cyclic portion ofthe cycloalkyl group or substituted cycloalkyl group comprises no morethan two ring structures fused together when L is a divalent linkinggroup, v is 1, and R₂ is a cycloalkyl group or a substituted cycloalkylgroup.

In a second embodiment, the invention provides a compound conforming tothe structure of Formula (C)

wherein R₁₀₁ is selected from the group consisting of a cyclopentylgroup and moieties conforming to the structure of Formula (CI); Formula(CI) is

R₁₀₅ is selected from the group consisting of hydrogen and halogens; xis a positive integer; each M₁ is a metal cation; y is the valence ofthe cation; z is a positive integer; b is zero or a positive integer;when b is a positive integer, each Q₁ is a negatively-charged counterionand a is the valence of the negatively-charged counterion; and thevalues of x, y, z, a, and b satisfy the equation x+(ab)=yz

In a third embodiment, the invention provides a compound conforming tothe structure of Formula (CX)

wherein R₁₁₁ is selected from the group consisting of a cyclopentylgroup and moieties conforming to the structure of Formula (CXI); R₁₁₂ isselected from the group consisting of hydrogen and hydroxy; Formula(CXI) is

R₁₁₅ is selected from the group consisting of hydrogen, a halogen,methoxy, and phenyl; x is a positive integer; each M₁ is a metal cation;y is the valence of the cation; z is a positive integer; b is zero or apositive integer; when b is a positive integer, each Q₁ is anegatively-charged counterion and a is the valence of thenegatively-charged counterion; and the values of x, y, z, a, and bsatisfy the equation x+(ab)=yz; provided if R₁₁₅ is hydrogen, then R₁₁₂is hydrogen, x is 1, M₁ is a lithium cation, y is 1, z is 1, and b iszero; and provided if R₁₁₅ is a methoxy group, then R₁₁₂ is a hydroxygroup.

In a fourth embodiment, the invention provides a compound conforming tothe structure of Formula (CXX)

wherein x is a positive integer; each M₁ is a cation of a metal selectedfrom the group consisting of alkali metals, alkaline earth metals, andzinc; y is the valence of the cation; z is a positive integer; b is zeroor a positive integer; when b is a positive integer, each Q₁ is anegatively-charged counterion and a is the valence of thenegatively-charged counterion; and the values of x, y, z, a, and bsatisfy the equation x+(ab)=yz.

DETAILED DESCRIPTION OF THE INVENTION

The following definitions are provided to define several of the termsused throughout this application.

As used herein, the term “substituted alkyl groups” refers to univalentfunctional groups derived from substituted alkanes by removal of ahydrogen atom from a carbon atom of the alkane. In this definition, theterm “substituted alkanes” refers to compounds derived from acyclicunbranched and branched hydrocarbons in which (1) one or more of thehydrogen atoms of the hydrocarbon is replaced with a non-hydrogen atom(e.g., a halogen atom) or a non-alkyl functional group (e.g., a hydroxygroup, aryl group, or heteroaryl group) and/or (2) the carbon-carbonchain of the hydrocarbon is interrupted by an oxygen atom (as in anether), a nitrogen atom (as in an amine), or a sulfur atom (as in asulfide).

As used herein, the term “substituted cycloalkyl groups” refers tounivalent functional groups derived from substituted cycloalkanes byremoval of a hydrogen atom from a carbon atom of the cycloalkane. Inthis definition, the term “substituted cycloalkanes” refers to compoundsderived from saturated monocyclic and polycyclic hydrocarbons (with orwithout side chains) in which (1) one or more of the hydrogen atoms ofthe hydrocarbon is replaced with a non-hydrogen atom (e.g., a halogenatom) or a non-alkyl functional group (e.g., a hydroxy group, arylgroup, or heteroaryl group) and/or (2) the carbon-carbon chain of thehydrocarbon is interrupted by an oxygen atom, a nitrogen atom, or asulfur atom.

As used herein, the term “substituted alkoxy groups” refers to univalentfunctional groups derived from substituted hydroxyalkanes by removal ofa hydrogen atom from a hydroxy group. In this definition, the term“substituted hydroxyalkanes” refers to compounds having one or morehydroxy groups bonded to a substituted alkane, and the term “substitutedalkane” is defined as it is above in the definition of substituted alkylgroups.

As used herein, the term “substituted aryl groups” refers to univalentfunctional groups derived from substituted arenes by removal of ahydrogen atom from a ring carbon atom. In this definition, the term“substituted arenes” refers to compounds derived from monocyclic andpolycyclic aromatic hydrocarbons in which one or more of the hydrogenatoms of the hydrocarbon is replaced with a non-hydrogen atom (e.g., ahalogen atom) or a non-alkyl functional group (e.g., a hydroxy group).

As used herein, the term “substituted heteroaryl groups” refers tounivalent functional groups derived from substituted heteroarenes byremoval of a hydrogen atom from a ring atom. In this definition, theterm “substituted heteroarenes” refers to compounds derived frommonocyclic and polycyclic aromatic hydrocarbons in which (1) one or moreof the hydrogen atoms of the hydrocarbon is replaced with a non-hydrogenatom (e.g., a halogen atom) or a non-alkyl functional group (e.g., ahydroxy group) and (2) at least one methine group (—C═) of thehydrocarbon is replaced by a trivalent heteroatom and/or at least onevinylidene group (—CH═CH—) of the hydrocarbon is replaced by a divalentheteroatom.

As used herein, the term “alkanediyl groups” refers to divalentfunctional groups derived from alkanes by removal of two hydrogen atomsfrom the alkane. These hydrogen atoms can be removed from the samecarbon atom on the alkane (as in ethane-1,1-diyl) or from differentcarbon atoms (as in ethane-1,2-diyl).

As used herein, the term “substituted alkanediyl groups” refers todivalent functional groups derived from substituted alkanes by removalof two hydrogen atoms from the alkane. These hydrogen atoms can beremoved from the same carbon atom on the substituted alkane (as in2-fluoroethane-1,1-diyl) or from different carbon atoms (as in1-fluoroethane-1,2-diyl). In this definition, the term “substitutedalkanes” has the same meaning as set forth above in the definition ofsubstituted alkyl groups.

As used herein, the term “cycloalkanediyl groups” refers to divalentfunctional groups derived from cycloalkanes by removal of two hydrogenatoms from the cycloalkane. These hydrogen atoms can be removed from thesame carbon atom on the cycloalkane or from different carbon atoms.

As used herein, the term “substituted cycloalkanediyl groups” refers todivalent functional groups derived from substituted cycloalkanes byremoval of two hydrogen atoms from the alkane. In this definition, theterm “substituted cycloalkanes” has the same meaning as set forth abovein the definition of substituted cycloalkyl groups.

As used herein, the term “arenediyl groups” refers to divalentfunctional groups derived from arenes (monocyclic and polycyclicaromatic hydrocarbons) by removal of two hydrogen atoms from ring carbonatoms.

As used herein, the term “substituted arenediyl groups” refers todivalent functional groups derived from substituted arenes by removal oftwo hydrogen atoms from ring carbon atoms. In this definition, the term“substituted arenes” refers to compounds derived from monocyclic andpolycyclic aromatic hydrocarbons in which one or more of the hydrogenatoms of the hydrocarbon is replaced with a non-hydrogen atom (e.g., ahalogen atom) or a non-alkyl functional group (e.g., a hydroxy group).

As used herein, the term “heteroarenediyl groups” refers to divalentfunctional groups derived from heteroarenes by removal of two hydrogenatoms from ring atoms. In this definition, the term “heteroarenes”refers to compounds derived from monocyclic and polycyclic aromatichydrocarbons in which at least one methine group (—C═) of thehydrocarbon is replaced by a trivalent heteroatom and/or at least onevinylidene group (—CH═CH—) of the hydrocarbon is replaced by a divalentheteroatom.

As used herein, the term “substituted heteroarenediyl groups” refers todivalent functional groups derived from substituted heteroarenes byremoval of two hydrogen atoms from ring atoms. In this definition, theterm “substituted heteroarenes” has the same meaning as set forth abovein the definition of substituted heteroaryl groups.

As used herein, the term “alkanetriyl groups” refers to trivalentfunctional groups derived from alkanes by removal of three hydrogenatoms from the alkane. These hydrogen atoms can be removed from the samecarbon atom on the alkane or from different carbon atoms.

As used herein, the term “substituted alkanetriyl groups” refers totrivalent functional groups derived from substituted alkanes by removalof three hydrogen atoms from the alkane. These hydrogen atoms can beremoved from the same carbon atom on the substituted alkane or fromdifferent carbon atoms. In this definition, the term “substitutedalkanes” has the same meaning as set forth above in the definition ofsubstituted alkyl groups.

As used herein, the term “cycloalkanetriyl groups” refers to trivalentfunctional groups derived from cycloalkanes by removal of three hydrogenatoms from the cycloalkane.

As used herein, the term “substituted cycloalkanetriyl groups” refers totrivalent functional groups derived from substituted cycloalkanes byremoval of three hydrogen atoms from the alkane. In this definition, theterm “substituted cycloalkanes” has the same meaning as set forth abovein the definition of substituted cycloalkyl groups.

As used herein, the term “arenetriyl groups” refers to trivalentfunctional groups derived from arenes (monocyclic and polycyclicaromatic hydrocarbons) by removal of three hydrogen atoms from ringcarbon atoms.

As used herein, the term “substituted arenetriyl groups” refers totrivalent functional groups derived from substituted arenes by removalof three hydrogen atoms from ring carbon atoms. In this definition, theterm “substituted arenes” has the same meaning as set forth above in thedefinition of substituted arenediyl groups.

As used herein, the term “heteroarenetriyl groups” refers to trivalentfunctional groups derived from heteroarenes by removal of three hydrogenatoms from ring atoms. In this definition, the term “heteroarenes” hasthe same meaning as set forth above in the definition of heteroarenediylgroups.

As used herein, the term “substituted heteroarenetriyl groups” refers totrivalent functional groups derived from substituted heteroarenes byremoval of three hydrogen atoms from ring atoms. In this definition, theterm “substituted heteroarenes” has the same meaning as set forth abovein the definition of substituted heteroaryl groups.

In a first embodiment, the invention provides a thermoplastic polymercomposition comprising a thermoplastic polymer and a nucleating agent.The thermoplastic polymer of the thermoplastic polymer composition canbe any suitable thermoplastic polymer. As utilized herein, the term“thermoplastic polymer” is used to refer to a polymeric material thatwill melt upon exposure to sufficient heat to form a flowable liquid andwill return to a solidified state upon sufficient cooling. In theirsolidified state, such thermoplastic polymers exhibit either crystallineor semicrystalline morphology. Suitable thermoplastic polymers include,but are not limited to, polyolefins (e.g., polyethylenes,polypropylenes, polybutylenes, and any combinations thereof), polyamides(e.g., nylon), polyurethanes, polyesters (e.g., polyethyleneterephthalate), and the like, as well as any combinations thereof. Thesethermoplastic polymers can be in the form of powder, fluff, flake,prill, or pellet made from freshly-produced polymer, polymer regrind,post-consumer waste, or post-industrial waste.

In certain embodiments, the thermoplastic polymer can be a polyolefin,such as a polypropylene, a polyethylene, a polybutylene, apoly(4-methyl-1-pentene), and a poly(vinyl cyclohexane). In a preferredembodiment, the thermoplastic polymer is a polyolefin selected from thegroup consisting of polypropylene homopolymers (e.g., atacticpolypropylene, isotactic polypropylene, and syndiotactic polypropylene),polypropylene copolymers (e.g., polypropylene random copolymers),polypropylene impact copolymers, polyethylene, polyethylene copolymers,polybutylene, poly(4-methyl-1-pentene), and mixtures thereof. Suitablepolypropylene copolymers include, but are not limited to, randomcopolymers made from the polymerization of propylene in the presence ofa comonomer selected from the group consisting of ethylene, but-1-ene(i.e., 1-butene), and hex-1-ene (i.e., 1-hexene). In such polypropylenerandom copolymers, the comonomer can be present in any suitable amount,but typically is present in an amount of less than about 10 wt. % (e.g.,about 1 to about 7 wt. %). Suitable polypropylene impact copolymersinclude, but are not limited to, those produced by the addition of acopolymer selected from the group consisting of ethylene-propylenerubber (EPR), ethylenepropylene-diene monomer (EPDM), polyethylene, andplastomers to a polypropylene homopolymer or polypropylene randomcopolymer. In such polypropylene impact copolymers, the copolymer can bepresent in any suitable amount, but typically is present in an amount offrom about 5 to about 25 wt. %.

In another preferred embodiment, the thermoplastic polymer can be apolyethylene. Suitable polyethylenes include, but are not limited to,low density polyethylene, linear low density polyethylene, mediumdensity polyethylene, high density polyethylene, and combinationsthereof. In certain preferred embodiments, the thermoplastic polymer isselected from the group consisting of linear low density polyethylene,high density polyethylene, and mixtures thereof. In another preferredembodiment, the thermoplastic polymer is a high density polyethylene.

The high density polyethylene polymers suitable for use in the inventiongenerally have a density of greater than about 0.940 g/cm³. There is noupper limit to the suitable density of the polymer, but high densitypolyethylene polymers typically have a density that is less than about0.980 g/cm³ (e.g., less than about 0.975 g/cm³).

The high density polyethylene polymers suitable for use in the inventioncan be either homopolymers or copolymers of ethylene with one or moreα-olefins. Suitable α-olefins include, but are not limited to, 1-butene,1-hexene, 1-octene, 1-decene, and 4-methyl-1-pentene. The comonomer canbe present in the copolymer in any suitable amount, such as an amount ofabout 5% by weight or less (e.g., about 3 mol. % or less). As will beunderstood by those of ordinary skill in the art, the amount ofcomonomer suitable for the copolymer is largely driven by the end usefor the copolymer and the required or desired polymer propertiesdictated by that end use.

The high density polyethylene polymers suitable for use in the inventioncan be produced by any suitable process. For example, the polymers canbe produced by a free radical process using very high pressures asdescribed, for example, in U.S. Pat. No. 2,816,883 (Larchar et al.), butthe polymers typically are produced in a “low pressure” catalyticprocess. In this context, the term “low pressure” is used to denoteprocesses carried out at pressures less than 6.9 MPa (e.g., 1,000 psig),such as 1.4-6.9 MPa (200-1,000 psig). Examples of suitable low pressurecatalytic processes include, but are not limited to, solutionpolymerization processes (i.e., processes in which the polymerization isperformed using a solvent for the polymer), slurry polymerizationprocesses (i.e., processes in which the polymerization is performedusing a hydrocarbon liquid in which the polymer does not dissolve orswell), gas-phase polymerization processes (e.g., processes in which thepolymerization is performed without the use of a liquid medium ordiluent), or a staged reactor polymerization process. The suitablegas-phase polymerization processes also include the so-called “condensedmode” or “super-condensed mode” processes in which a liquid hydrocarbonis introduced into the fluidized-bed to increase the absorption of theheat producing during the polymerization process. In these condensedmode and super-condensed mode processes, the liquid hydrocarbontypically is condensed in the recycle stream and reused in the reactor.The staged reactor processes can utilize a combination of slurry processreactors (tanks or loops) that are connected in series, parallel, or acombination of series or parallel so that the catalyst (e.g., chromiumcatalyst) is exposed to more than one set of reaction conditions. Stagedreactor processes can also be carried out by combining two loops inseries, combining one or more tanks and loops in series, using multiplegas-phase reactors in series, or a loop-gas phase arrangement. Becauseof their ability to expose the catalyst to different sets of reactorconditions, staged reactor processes are often used to producemultimodal polymers, such as those discussed below. Suitable processesalso include those in which a pre-polymerization step is performed. Inthis pre-polymerization step, the catalyst typically is exposed to thecocatalyst and ethylene under mild conditions in a smaller, separatereactor, and the polymerization reaction is allowed to proceed until thecatalyst comprises a relatively small amount (e.g., about 5% to about30% of the total weight) of the resulting composition. Thispre-polymerized catalyst is then introduced to the large-scale reactorin which the polymerization is to be performed.

The high density polyethylene polymers suitable for use in the inventioncan be produced using any suitable catalyst or combination of catalysts.Suitable catalysts include transition metal catalysts, such as supportedreduced molybdenum oxide, cobalt molybdate on alumina, chromium oxide,and transition metal halides. Chromium oxide catalysts typically areproduced by impregnating a chromium compound onto a porous, high surfacearea oxide carrier, such as silica, and then calcining it in dry air at500-900° C. This converts the chromium into a hexavalent surfacechromate ester or dichromate ester. The chromium oxide catalysts can beused in conjunction with metal alkyl cocatalysts, such as alkyl boron,alkyl aluminum, alkyl zinc, and alkyl lithium. Supports for the chromiumoxide include silica, silica-titania, silica-alumina, alumina, andaluminophosphates. Further examples of chromium oxide catalysts includethose catalysts produced by depositing a lower valent organochromiumcompound, such as bis(arene) Cr⁰, allyl Cr²⁺ and CO⁺, beta stabilizedalkyls of Cr²⁺ and CO⁺, and bis(cyclopentadienyl) Cr²⁺, onto a chromiumoxide catalyst, such as those described above. Suitable transition metalcatalysts also include supported chromium catalysts such as those basedon chromocene or a silylchromate (e.g., bi(trisphenylsilyl)chromate).These chromium catalysts can be supported on any suitable high surfacearea support such as those described above for the chromium oxidecatalysts, with silica typically being used. The supported chromiumcatalysts can also be used in conjunction with cocatalysts, such as themetal alkyl cocatalysts listed above for the chromium oxide catalysts.Suitable transition metal halide catalysts include titanium (III)halides (e.g., titanium (III) chloride), titanium (IV) halides (e.g.,titanium (IV) chloride), vanadium halides, zirconium halides, andcombinations thereof. These transition metal halides are often supportedon a high surface area solid, such as magnesium chloride. The transitionmetal halide catalysts are typically used in conjunction with analuminum alkyl cocatalyst, such as trimethylaluminum (i.e., Al(CH₃)₃) ortriethylaluminum (i.e., Al(C₂H₅)₃). These transition metal halides mayalso be used in staged reactor processes. Suitable catalysts alsoinclude metallocene catalysts, such as cyclopentadienyl titanium halides(e.g., cyclopentadienyl titanium chlorides), cyclopentadienyl zirconiumhalides (e.g., cyclopentadienyl zirconium chlorides), cyclopentadienylhafnium halides (e.g., cyclopentadienyl hafnium chlorides), andcombinations thereof. Metallocene catalysts based on transition metalscomplexed with indenyl or fluorenyl ligands are also known and can beused to produce high density polyethylene polymers suitable for use inthe invention. The catalysts typically contain multiple ligands, and theligands can be substituted with various groups (e.g., n-butyl group) orlinked with bridging groups, such as —CH₂CH₂— or >SiPh₂. The metallocenecatalysts typically are used in conjunction with a cocatalyst, such asmethyl aluminoxane (i.e., (Al(CH₃)_(x)O_(y))_(n). Other cocatalystsinclude those described in U.S. Pat. No. 5,919,983 (Rosen et al.), U.S.Pat. No. 6,107,230 (McDaniel et al.), U.S. Pat. No. 6,632,894 (McDanielet al.), and U.S. Pat. No. 6,300,271 (McDaniel et al). Other “singlesite” catalysts suitable for use in producing high density polyethyleneinclude diimine complexes, such as those described in U.S. Pat. No.5,891,963 (Brookhart et al.).

The high density polyethylene polymers suitable for use in the inventioncan have any suitable molecular weight (e.g., weight average molecularweight). For example, the weight average molecular weight of the highdensity polyethylene can be from 20,000 g/mol to about 1,000,000 g/molor more. As will be understood by those of ordinary skill in the art,the suitable weight average molecular weight of the high densitypolyethylene will depend, at least in part, on the particularapplication or end use for which the polymer is destined. For example, ahigh density polyethylene polymer intended for blow molding applicationscan have a weight average molecular weight of about 100,000 g/mol toabout 1,000,000 g/mol. A high density polyethylene polymer intended forpipe applications or film applications can have a weight averagemolecular weight of about 100,000 g/mol to about 500,000 g/mol. A highdensity polyethylene polymer intended for injection molding applicationscan have a weight average molecular weight of about 20,000 g/mol toabout 80,000 g/mol. A high density polyethylene polymer intended forwire insulation applications, cable insulation applications, tapeapplications, or filament applications can have a weight averagemolecular weight of about 80,000 g/mol to about 400,000 g/mol. A highdensity polyethylene polymer intended for rotomolding applications canhave a weight average molecular weight of about 50,000 g/mol to about150,000 g/mol.

The high density polyethylene polymers suitable for use in the inventioncan also have any suitable polydispersity, which is defined as the valueobtained by dividing the weight average molecular weight of the polymerby the number average molecular weight of the polymer. For example, thehigh density polyethylene polymer can have a polydispersity of greaterthan 2 to about 100. As understood by those skilled in the art, thepolydispersity of the polymer is heavily influenced by the catalystsystem used to produce the polymer, with the metallocene and other“single site” catalysts generally producing polymers with relatively lowpolydispersity and narrow molecular weight distributions and the othertransition metal catalysts (e.g., chromium catalysts) producing polymerswith higher polydispersity and broader molecular weight distributions.The high density polyethylene polymers suitable for use in the inventioncan also have a multimodal (e.g., bimodal) molecular weightdistribution. For example, the polymer can have a first fraction havinga relatively low molecular weight and a second fraction having arelatively high molecular weight. The difference between the weightaverage molecular weight of the fractions in the polymer can be anysuitable amount. In fact, it is not necessary for the difference betweenthe weight average molecular weights to be large enough that twodistinct molecular weight fractions can be resolved using gel permeationchromatography (GPC). However, in certain multimodal polymers, thedifference between the weight average molecular weights of the fractionscan be great enough that two or more distinct peaks can be resolved fromthe GPC curve for the polymer. In this context, the term “distinct” doesnot necessarily mean that the portions of the GPC curve corresponding toeach fraction do not overlap, but is merely meant to indicate that adistinct peak for each fraction can be resolved from the GPC curve forthe polymer. The multimodal polymers suitable for use in the inventioncan be produced using any suitable process. As noted above, themultimodal polymers can be produced using staged reactor processes. Onesuitable example would be a staged solution process incorporating aseries of stirred tanks. Alternatively, the multimodal polymers can beproduced in a single reactor using a combination of catalysts each ofwhich is designed to produce a polymer having a different weight averagemolecular weight.

The high density polyethylene polymers suitable for use in the inventioncan have any suitable melt index. For example, the high densitypolyethylene polymer can have a melt index of about 0.01 dg/min to about40 dg/min. As with the weight average molecular weight, those ofordinary skill in the art understand that the suitable melt index forthe high density polyethylene polymer will depend, at least in part, onthe particular application or end use for which the polymer is destined.Thus, for example, a high density polyethylene polymer intended for blowmolding applications can have a melt index of about 0.01 dg/min to about1 dg/min. A high density polyethylene polymer intended for blown filmapplications can have a melt index of about 0.5 dg/min to about 3dg/min. A high density polyethylene polymer intended for cast filmapplications can have a melt index of about 2 dg/min to about 10 dg/min.A high density polyethylene polymer intended for pipe applications canhave a melt index of about 2 dg/min to about 40 dg/min. A high densitypolyethylene polymer intended for injection molding applications canhave a melt index of about 2 dg/min to about 80 dg/min. A high densitypolyethylene polymer intended for rotomolding applications can have amelt index of about 0.5 dg/min to about 10 dg/min. A high densitypolyethylene polymer intended for tape applications can have a meltindex of about 0.2 dg/min to about 4 dg/min. A high density polyethylenepolymer intended for filament applications can have a melt index ofabout 1 dg/min to about 20 dg/min. The melt index of the polymer ismeasured using ASTM Standard D1238-04c.

The high density polyethylene polymers suitable for use in the inventiongenerally do not contain high amounts of long-chain branching. The term“long-chain branching” is used to refer to branches that are attached tothe polymer chain and are of sufficient length to affect the rheology ofthe polymer (e.g., branches of about 130 carbons or more in length). Ifdesired for the application in which the polymer is to be used, the highdensity polyethylene polymer can contain small amounts of long-chainbranching. However, the high density polyethylene polymers suitable foruse in the invention typically contain very little long-chain branching(e.g., less than about 1 long-chain branch per 10,000 carbons, less thanabout 0.5 long-chain branches per 10,000 carbons, less than about 0.1long-chain branches per 10,000 carbons, or less than about 0.01long-chain branches per 10,000 carbons).

The medium density polyethylene polymers suitable for use in theinvention generally have a density of about 0.926 g/cm³ to about 0.940g/cm³. The term “medium density polyethylene” is used to refer topolymers of ethylene that have a density between that of high densitypolyethylene and linear low density polyethylene and contain relativelyshort branches, at least as compared to the long branches present in lowdensity polyethylene polymers produced by the free radicalpolymerization of ethylene at high pressures.

The medium density polyethylene polymers suitable for use in theinvention generally are copolymers of ethylene and at least oneα-olefin, such as 1-butene, 1-hexene, 1-octene, 1-decene, and4-methyl-1-pentene. The α-olefin comonomer can be present in anysuitable amount, but typically is present in an amount of less thanabout 8% by weight (e.g., less than about 5 mol %). As will beunderstood by those of ordinary skill in the art, the amount ofcomonomer suitable for the copolymer is largely driven by the end usefor the copolymer and the required or desired polymer propertiesdictated by that end use.

The medium density polyethylene polymers suitable for use in theinvention can be produced by any suitable process. Like the high densitypolyethylene polymers, the medium density polyethylene polymerstypically are produced in “low pressure” catalytic processes such as anyof the processes described above in connection with the high densitypolyethylene polymers suitable for use in the invention. Examples ofsuitable processes include, but are not limited to, gas-phasepolymerization processes, solution polymerization processes, slurrypolymerization processes, and staged reactor processes. Suitable stagedreactor processes can incorporate any suitable combination of thegas-phase, solution, and slurry polymerization processes describedabove. As with high density polyethylene polymers, staged reactorprocesses are often used to produce multimodal polymers.

The medium density polyethylene polymers suitable for use in theinvention can be produced using any suitable catalyst or combination ofcatalysts. For example, the polymers can be produced using Zieglercatalysts, such as transition metal (e.g., titanium) halides or estersused in combination with organoaluminum compounds (e.g.,triethylaluminum). These Ziegler catalysts can be supported on, forexample, magnesium chloride, silica, alumina, or magnesium oxide. Themedium density polyethylene polymers suitable for use in the inventioncan also be produced using so-called “dual Ziegler catalysts,” whichcontain one catalyst species for dimerizing ethylene into 1-butene(e.g., a combination of a titanium ester and triethylaluminum) andanother catalyst for copolymerization of ethylene and the generated1-butene (e.g., titanium chloride supported on magnesium chloride). Themedium density polyethylene polymers suitable for use in the inventioncan also be produced using chromium oxide catalysts, such as thoseproduced by depositing a chromium compound onto a silica-titaniasupport, oxidizing the resulting catalyst in a mixture of oxygen andair, and then reducing the catalyst with carbon monoxide. These chromiumoxide catalysts typically are used in conjunction with cocatalysts suchas trialkylboron or trialkylaluminum compounds. The chromium oxidecatalysts can also be used in conjunction with a Ziegler catalyst, suchas a titanium halide- or titanium ester-based catalyst. The mediumdensity polyethylene polymers suitable for use in the invention can alsobe produced using supported chromium catalysts such as those describedabove in the discussion of catalysts suitable for making high densitypolyethylene. The medium density polyethylene polymers suitable for usein the invention can also be produced using metallocene catalysts.Several different types of metallocene catalysts can be used. Forexample, the metallocene catalyst can contain a bis(metallocene) complexof zirconium, titanium, or hafnium with two cyclopentadienyl rings andmethylaluminoxane. As with the catalysts used in high densitypolyethylene production, the ligands can be substituted with variousgroups (e.g., n-butyl group) or linked with bridging groups. Anotherclass of metallocene catalysts that can be used are composed ofbis(metallocene) complexes of zirconium or titanium and anions ofperfluorinated boronaromatic compounds. A third class of metallocenecatalysts that can be used are referred to as constrained-geometrycatalysts and contain monocyclopentadienyl derivatives of titanium orzirconium in which one of the carbon atoms in the cyclopentadienyl ringis linked to the metal atom by a bridging group. These complexes areactivated by reacting them with methylaluminoxane or by forming ioniccomplexes with noncoordinative anions, such as B(C₆F₅)₄— orB(C₆F₅)₃CH₃—. A fourth class of metallocene catalysts that can be usedare metallocene-based complexes of a transition metal, such as titanium,containing one cyclopentadienyl ligand in combination with anotherligand, such as a phosphinimine or —O—SiR₃. This class of metallocenecatalyst is also activated with methylaluminoxane or a boron compound.Other catalysts suitable for use in making the medium densitypolyethylene suitable for use in the invention include, but are notlimited to, the catalysts disclosed in U.S. Pat. No. 6,649,558.

The medium density polyethylene polymers suitable for use in theinvention can have any suitable compositional uniformity, which is aterm used to describe the uniformity of the branching in the copolymermolecules of the polymer. Many commercially-available medium densitypolyethylene polymers have a relatively low compositional uniformity inwhich the high molecular weight fraction of the polymer containsrelatively little of the α-olefin comonomer and has relatively littlebranching while the low molecular weight fraction of the polymercontains a relatively high amount of the α-olefin comonomer and has arelatively large amount of branching. Alternatively, another set ofmedium density polyethylene polymers have a relatively low compositionaluniformity in which the high molecular weight fraction of the polymercontains a relatively high amount of the α-olefin comonomer while thelow molecular weight fraction of the polymer contains relatively littleof the α-olefin comonomer. The compositional uniformity of the polymercan be measured using any suitable method, such as temperature risingelution fractionation.

The medium density polyethylene polymers suitable for use in theinvention can have any suitable molecular weight. For example, thepolymer can have a weight average molecular weight of about 50,000 g/molto about 200,000 g/mol. As will be understood by those of ordinary skillin the art, the suitable weight average molecular weight of the mediumdensity polyethylene will depend, at least in part, on the particularapplication or end use for which the polymer is destined.

The medium density polyethylene polymers suitable for use in theinvention can also have any suitable polydispersity. Many commerciallyavailable medium density polyethylene polymers have a polydispersity ofabout 2 to about 30. The medium density polyethylene polymers suitablefor use in the invention can also have a multimodal (e.g., bimodal)molecular weight distribution. For example, the polymer can have a firstfraction having a relatively low molecular weight and a second fractionhaving a relatively high molecular weight. As with the high densitypolyethylene polymers suitable for use in the invention, the differencebetween the weight average molecular weight of the fractions in themultimodal medium density polyethylene polymer can be any suitableamount. In fact, it is not necessary for the difference between theweight average molecular weights to be large enough that two distinctmolecular weight fractions can be resolved using gel permeationchromatography (GPC). However, in certain multimodal polymers, thedifference between the weight average molecular weights of the fractionscan be great enough that two or more distinct peaks can be resolved fromthe GPC curve for the polymer. In this context, the term “distinct” doesnot necessarily mean that the portions of the GPC curve corresponding toeach fraction do not overlap, but is merely meant to indicate that adistinct peak for each fraction can be resolved from the GPC curve forthe polymer. The multimodal polymers suitable for use in the inventioncan be produced using any suitable process. As noted above, themultimodal polymers can be produced using staged reactor processes. Onesuitable example would be a staged solution process incorporating aseries of stirred tanks. Alternatively, the multimodal polymers can beproduced in a single reactor using a combination of catalysts each ofwhich is designed to produce a polymer having a different weight averagemolecular weight

The medium density polyethylene polymers suitable for use in theinvention can have any suitable melt index. For example, the mediumdensity polyethylene polymer can have a melt index of about 0.01 dg/minto about 200 dg/min. As with the weight average molecular weight, thoseof ordinary skill in the art understand that the suitable melt index forthe medium density polyethylene polymer will depend, at least in part,on the particular application or end use for which the polymer isdestined. Thus, for example, a medium density polyethylene polymerintended for blow molding applications or pipe applications can have amelt index of about 0.01 dg/min to about 1 dg/min. A medium densitypolyethylene polymer intended for blown film applications can have amelt index of about 0.5 dg/min to about 3 dg/min. A medium densitypolyethylene polymer intended for cast film applications can have a meltindex of about 2 dg/min to about 10 dg/min. A medium densitypolyethylene polymer intended for injection molding applications canhave a melt index of about 6 dg/min to about 200 dg/min. A mediumdensity polyethylene polymer intended for rotomolding applications canhave a melt index of about 4 dg/min to about 7 dg/min. A medium densitypolyethylene polymer intended for wire and cable insulation applicationscan have a melt index of about 0.5 dg/min to about 3 dg/min. The meltindex of the polymer is measured using ASTM Standard D1238-04c.

The medium density polyethylene polymers suitable for use in theinvention generally do not contain a significant amount of long-chainbranching. For example, the medium density polyethylene polymerssuitable for use in the invention generally contain less than about 0.1long-chain branches per 10,000 carbon atoms (e.g., less than about 0.002long-chain branches per 100 ethylene units) or less than about 0.01long-chain branches per 10,000 carbon atoms.

The linear low density polyethylene polymers suitable for use in theinvention generally have a density of 0.925 g/cm³ or less (e.g., about0.910 g/cm³ to about 0.925 g/cm³). The term “linear low densitypolyethylene” is used to refer to lower density polymers of ethylenehaving relatively short branches, at least as compared to the longbranches present in low density polyethylene polymers produced by thefree radical polymerization of ethylene at high pressures.

The linear low density polyethylene polymers suitable for use in theinvention generally are copolymers of ethylene and at least oneα-olefin, such as 1-butene, 1-hexene, 1-octene, 1-decene, and4-methyl-1-pentene. The α-olefin comonomer can be present in anysuitable amount, but typically is present in an amount of less thanabout 6 mol. % (e.g., about 2 mol % to about 5 mol %). As will beunderstood by those of ordinary skill in the art, the amount ofcomonomer suitable for the copolymer is largely driven by the end usefor the copolymer and the required or desired polymer propertiesdictated by that end use.

The linear low density polyethylene polymers suitable for use in theinvention can be produced by any suitable process. Like the high densitypolyethylene polymers, the linear low density polyethylene polymerstypically are produced in “low pressure” catalytic processes such as anyof the processes described above in connection with the high densitypolyethylene polymers suitable for use in the invention. Suitableprocesses include, but are not limited to, gas-phase polymerizationprocesses, solution polymerization processes, slurry polymerizationprocesses, and staged reactor processes. Suitable staged reactorprocesses can incorporate any suitable combination of the gas-phase,solution, and slurry polymerization processes described above. As withhigh density polyethylene polymers, staged reactor processes are oftenused to produce multimodal polymers.

The linear low density polyethylene polymers suitable for use in theinvention can be produced using any suitable catalyst or combination ofcatalysts. For example, the polymers can be produced using Zieglercatalysts, such as transition metal (e.g., titanium) halides or estersused in combination with organoaluminum compounds (e.g.,triethylaluminum). These Ziegler catalysts can be supported on, forexample, magnesium chloride, silica, alumina, or magnesium oxide. Thelinear low density polyethylene polymers suitable for use in theinvention can also be produced using so-called “dual Ziegler catalysts,”which contain one catalyst species for dimerizing ethylene into 1-butene(e.g., a combination of a titanium ester and triethylaluminum) andanother catalyst for copolymerization of ethylene and the generated1-butene (e.g., titanium chloride supported on magnesium chloride). Thelinear low density polyethylene polymers suitable for use in theinvention can also be produced using chromium oxide catalysts, such asthose produced by depositing a chromium compound onto a silica-titaniasupport, oxidizing the resulting catalyst in a mixture of oxygen andair, and then reducing the catalyst with carbon monoxide. These chromiumoxide catalysts typically are used in conjunction with cocatalysts suchas trialkylboron or trialkylaluminum compounds. The chromium oxidecatalysts can also be used in conjunction with a Ziegler catalyst, suchas a titanium halide- or titanium ester-based catalyst. The linear lowdensity polyethylene polymers suitable for use in the invention can alsobe produced using supported chromium catalysts such as those describedabove in the discussion of catalysts suitable for making high densitypolyethylene. The linear low density polyethylene suitable for use inthe invention can also be produced using metallocene catalysts. Severaldifferent types of metallocene catalysts can be used. For example, themetallocene catalyst can contain a bis(metallocene) complex ofzirconium, titanium, or hafnium with two cyclopentadienyl rings andmethylaluminoxane. As with the catalysts used in high densitypolyethylene production, the ligands can be substituted with variousgroups (e.g., n-butyl group) or linked with bridging groups. Anotherclass of metallocene catalysts that can be used are composed ofbis(metallocene) complexes of zirconium or titanium and anions ofperfluorinated boronaromatic compounds. A third class of metallocenecatalysts that can be used are referred to as constrained-geometrycatalysts and contain monocyclopentadienyl derivatives of titanium orzirconium in which one of the carbon atoms in the cyclopentadienyl ringis linked to the metal atom by a bridging group. These complexes areactivated by reacting them with methylaluminoxane or by forming ioniccomplexes with noncoordinative anions, such as B(C₆F₅)₄— orB(C₆F₅)₃CH₃—. A fourth class of metallocene catalysts that can be usedare metallocene-based complexes of a transition metal, such as titanium,containing one cyclopentadienyl ligand in combination with anotherligand, such as a phosphinimine or —O—SiR₃. This class of metallocenecatalyst is also activated with methylaluminoxane or a boron compound.Other catalysts suitable for use in making the linear low densitypolyethylene suitable for use in the invention include, but are notlimited to, the catalysts disclosed in U.S. Pat. No. 6,649,558.

The linear low density polyethylene polymers suitable for use in theinvention can have any suitable compositional uniformity, which is aterm used to describe the uniformity of the branching in the copolymermolecules of the polymer. Many commercially-available linear low densitypolyethylene polymers have a relatively low compositional uniformity inwhich the high molecular weight fraction of the polymer containsrelatively little of the α-olefin comonomer and has relatively littlebranching while the low molecular weight fraction of the polymercontains a relatively high amount of the α-olefin comonomer and has arelatively large amount of branching. Alternatively, another set oflinear low density polyethylene polymers have a relatively lowcompositional uniformity in which the high molecular weight fraction ofthe polymer contains a relatively high amount of the α-olefin comonomerwhile the low molecular weight fraction of the polymer containsrelatively little of the α-olefin comonomer. The compositionaluniformity of the polymer can be measured using any suitable method,such as temperature rising elution fractionation.

The linear low density polyethylene polymers suitable for use in theinvention can have any suitable molecular weight. For example, thepolymer can have a weight average molecular weight of about 20,000 g/molto about 250,000 g/mol. As will be understood by those of ordinary skillin the art, the suitable weight average molecular weight of the linearlow density polyethylene will depend, at least in part, on theparticular application or end use for which the polymer is destined.

The linear low density polyethylene polymers suitable for use in theinvention can also have any suitable polydispersity. Many commerciallyavailable linear low density polyethylene polymers have a relativelynarrow molecular weight distribution and thus a relatively lowpolydispersity, such as about 2 to about 5 (e.g., about 2.5 to about 4.5or about 3.5 to about 4.5). The linear low density polyethylene polymerssuitable for use in the invention can also have a multimodal (e.g.,bimodal) molecular weight distribution. For example, the polymer canhave a first fraction having a relatively low molecular weight and asecond fraction having a relatively high molecular weight. As with thehigh density polyethylene polymers suitable for use in the invention,the difference between the weight average molecular weight of thefractions in the multimodal linear low density polyethylene polymer canbe any suitable amount. In fact, it is not necessary for the differencebetween the weight average molecular weights to be large enough that twodistinct molecular weight fractions can be resolved using gel permeationchromatography (GPC). However, in certain multimodal polymers, thedifference between the weight average molecular weights of the fractionscan be great enough that two or more distinct peaks can be resolved fromthe GPC curve for the polymer. In this context, the term “distinct” doesnot necessarily mean that the portions of the GPC curve corresponding toeach fraction do not overlap, but is merely meant to indicate that adistinct peak for each fraction can be resolved from the GPC curve forthe polymer. The multimodal polymers suitable for use in the inventioncan be produced using any suitable process. As noted above, themultimodal polymers can be produced using staged reactor processes. Onesuitable example would be a staged solution process incorporating aseries of stirred tanks. Alternatively, the multimodal polymers can beproduced in a single reactor using a combination of catalysts each ofwhich is designed to produce a polymer having a different weight averagemolecular weight

The linear low density polyethylene polymers suitable for use in theinvention can have any suitable melt index. For example, the linear lowdensity polyethylene polymer can have a melt index of about 0.01 dg/minto about 200 dg/min. As with the weight average molecular weight, thoseof ordinary skill in the art understand that the suitable melt index forthe linear low density polyethylene polymer will depend, at least inpart, on the particular application or end use for which the polymer isdestined. Thus, for example, a linear low density polyethylene polymerintended for blow molding applications or pipe applications can have amelt index of about 0.01 dg/min to about 1 dg/min. A linear low densitypolyethylene polymer intended for blown film applications can have amelt index of about 0.5 dg/min to about 3 dg/min. A linear low densitypolyethylene polymer intended for cast film applications can have a meltindex of about 2 dg/min to about 10 dg/min. A linear low densitypolyethylene polymer intended for injection molding applications canhave a melt index of about 6 dg/min to about 200 dg/min. A linear lowdensity polyethylene polymer intended for rotomolding applications canhave a melt index of about 4 dg/min to about 7 dg/min. A linear lowdensity polyethylene polymer intended for wire and cable insulationapplications can have a melt index of about 0.5 dg/min to about 3dg/min. The melt index of the polymer is measured using ASTM StandardD1238-04c.

The linear low density polyethylene polymers suitable for use in theinvention generally do not contain a significant amount of long-chainbranching. For example, the linear low density polyethylene polymerssuitable for use in the invention generally contain less than about 0.1long-chain branches per 10,000 carbon atoms (e.g., less than about 0.002long-chain branches per 100 ethylene units) or less than about 0.01long-chain branches per 10,000 carbon atoms.

The low density polyethylene polymers suitable for use in the inventiongenerally have a density of less than 0.935 g/cm³ and, in contrast tohigh density polyethylene, medium density polyethylene and linear lowdensity polyethylene, have a relatively large amount of long-chainbranching in the polymer.

The low density polyethylene polymers suitable for use in the inventioncan be either ethylene homopolymers or copolymers of ethylene and apolar comonomer. Suitable polar comonomers include, but are not limitedto, vinyl acetate, methyl acrylate, ethyl acrylate, and acrylic acid.These comonomers can be present in any suitable amount, with comonomercontents as high as 20% by weight being used for certain applications.As will be understood by those skilled in the art, the amount ofcomonomer suitable for the polymer is largely driven by the end use forthe polymer and the required or desired polymer properties dictated bythat end use.

The low density polyethylene polymers suitable for use in the inventioncan be produced using any suitable process, but typically the polymersare produced by the free-radical initiated polymerization of ethylene athigh pressure (e.g., about 81 to about 276 MPa) and high temperature(e.g., about 130 to about 330° C.). Any suitable free radical initiatorcan be used in such processes, with peroxides and oxygen being the mostcommon. The free-radical polymerization mechanism gives rise toshort-chain branching in the polymer and also to the relatively highdegree of long-chain branching that distinguishes low densitypolyethylene from other ethylene polymers (e.g., high densitypolyethylene and linear low density polyethylene). The polymerizationreaction typically is performed in an autoclave reactor (e.g., a stirredautoclave reactor), a tubular reactor, or a combination of such reactorspositioned in series.

The low density polyethylene polymers suitable for use in the inventioncan have any suitable molecular weight. For example, the polymer canhave a weight average molecular weight of about 30,000 g/mol to about500,000 g/mol. As will be understood by those of ordinary skill in theart, the suitable weight average molecular weight of the low densitypolyethylene will depend, at least in part, on the particularapplication or end use for which the polymer is destined. For example, alow density polyethylene polymer intended for blow molding applicationscan have a weight average molecular weight of about 80,000 g/mol toabout 200,000 g/mol. A low density polyethylene polymer intended forpipe applications can have a weight average molecular weight of about80,000 g/mol to about 200,000 g/mol. A low density polyethylene polymerintended for injection molding applications can have a weight averagemolecular weight of about 30,000 g/mol to about 80,000 g/mol. A lowdensity polyethylene polymer intended for film applications can have aweight average molecular weight of about 60,000 g/mol to about 500,000g/mol.

The low density polyethylene polymers suitable for use in the inventioncan have any suitable melt index. For example, the low densitypolyethylene polymer can have a melt index of about 0.2 to about 100dg/min. As noted above, the melt index of the polymer is measured usingASTM Standard D1238-04c.

As noted above, one of the major distinctions between low densitypolyethylene and other ethylene polymers is a relatively high degree oflong-chain branching within the polymer. The low density polyethylenepolymers suitable for use in the invention can exhibit any suitableamount of long-chain branching, such as about 0.01 or more long-chainbranches per 10,000 carbon atoms, about 0.1 or more long-chain branchesper 10,000 carbon atoms, about 0.5 or more long-chain branches per10,000 carbon atoms, about 1 or more long-chain branches per 10,000carbon atoms, or about 4 or more long-chain branches per 10,000 carbonatoms. While there is not a strict limit on the maximum extent oflong-chain branching that can be present in the low density polyethylenepolymers suitable for use in the invention, the long-chain branching inmany low density polyethylene polymers is less than about 100 long-chainbranches per 10,000 carbon atoms.

The thermoplastic polymer composition also comprises a nucleating agent.As utilized herein, the term “nucleating agent” is used to refer tocompounds or additives that form nuclei or provide sites for theformation and/or growth of crystals in a polymer as it solidifies from amolten state. In a first embodiment, the nucleating agent comprises acompound conforming to the structure of Formula (I)

In the structure of Formula (I), R₁ is selected from the groupconsisting of hydroxy, halogens, alkyl groups, substituted alkyl groups,alkoxy groups, substituted alkoxy groups, aryl groups, and substitutedaryl groups. The variable n is zero or a positive integer from 1 to 4. Lis a linking group comprising two or more atoms and at least one doublebond between two atoms in the linking group. The variable v is apositive integer from 1 to 3. R₂ is: (i) selected from the groupconsisting of alkyl groups, substituted alkyl groups, cycloalkyl groups,substituted cycloalkyl groups, aryl groups, substituted aryl groups,heteroaryl groups, and substituted heteroaryl groups when L is adivalent linking group and v is 1, (ii) selected from the groupconsisting of alkanediyl groups, substituted alkanediyl groups,cycloalkanediyl groups, substituted cycloalkanediyl groups, arenediylgroups, substituted arenediyl groups, heteroarenediyl groups, andsubstituted heteroarenediyl groups when L is a trivalent linking groupand v is 1, (iii) selected from the group consisting of alkanediylgroups, substituted alkanediyl groups, cycloalkanediyl groups,substituted cycloalkanediyl groups, arenediyl groups, substitutedarenediyl groups, heteroarenediyl groups, and substitutedheteroarenediyl groups when L is a divalent linking group and v is 2,and (iv) selected from the group consisting of alkanetriyl groups,substituted alkanetriyl groups, cycloalkanetriyl groups, substitutedcycloalkanetriyl groups, arenetriyl groups, substituted arenetriylgroups, heteroarenetriyl groups, and substituted heteroarenetriyl groupswhen L is a divalent linking group and v is 3. The variable x is apositive integer. Each M₁ is a metal cation; the variable y is thevalence of the cation; and the variable z is a positive integer. Thevariable b is zero or a positive integer. When b is a positive integer,each Q₁ is a negatively-charged counterion, and a is the valence of thenegatively-charged counterion. The values of v, x, y, z, a, and bsatisfy the equation (vx)+(ab)=yz. In the structure of Formula (I), thecyclic portion of the cycloalkyl group or substituted cycloalkyl groupcomprises no more than two ring structures fused together when L is adivalent linking group, v is 1, and R₂ is a cycloalkyl group or asubstituted cycloalkyl group.

In a preferred embodiment, R₁ is a halogen or hydroxy, with n=1 beingparticularly preferred. In a more specific embodiment, n can be 1, R₁can be hydroxy and attached to the aryl ring in the ortho positionrelative to the carboxylate group. In another preferred embodiment, n is0, meaning that the carboxylate-substituted aryl ring is not substitutedwith R₁ groups.

L is a linking group comprising two or more atoms and at least onedouble bond between two atoms in the linking group. With at least onedouble bond between two atoms in the linking group, two of the atoms inthe linking group are sp² hybridized and the sum of the bond anglesaround at least one of these atoms is approximately 360 degrees. Thepresence of the double bond within the liking group restricts rotationof the molecule around the double bond and, while not wishing to bebound to any particular theory, is believed to maintain the compound ina configuration that is more favorable for nucleation of the polymer. Ina series of preferred embodiments, L is selected from the groupconsisting of moieties conforming to the structure of one of Formulae(LA)-(LF) below

As can be seen from these structures, suitable linking groups compriseat least two atoms and a double bond between two atoms in the linkinggroup. With each of these L groups, any suitable end of the linkinggroup can be attached to the carboxylate-substituted aryl ring and theother end(s) can be attached to the group R₂. In a preferred embodiment,L is a moiety selecting from the group consisting of moieties conformingto the structure of Formulae (LA) and (LD). In a particularly preferredembodiment, L is a moiety conforming to the structure of Formula (LA).In such an embodiment, the moiety can have the nitrogen atom bonded tothe carboxylate-substituted aryl ring or the group R₂.

The group R₂ can be a monovalent, divalent, or trivalent moiety. Thevalence of R₂ depends on the valence of the linking group L and thenumber of carboxylate-substituted aryl rings in the compound. Thus, whenL is a divalent linking group, v is 1, and R₂ can be selected from thegroup consisting of moieties conforming to the structure of one ofFormulae (AA)-(AG) below. The structure of Formula (AA) is

In the structure of Formula (AA), the variable d is zero or a positiveinteger from 1 to 5, and each R₁₀ is independently selected from thegroup consisting of halogens, alkyl groups, substituted alkyl groups,alkoxy groups, substituted alkoxy groups, aryl groups, and substitutedaryl groups. The structure of Formula (AB) is

In the structure of Formula (AB), the variable h is zero or a positiveinteger from 1 to 10, and each R₁₃ is independently selected from thegroup consisting of halogens, alkyl groups, substituted alkyl groups,alkoxy groups, substituted alkoxy groups, aryl groups, and substitutedaryl groups. The structure of Formula (AC) is

In the structure of Formula (AC), the variable e is zero or a positiveinteger from 1 to 8, and each R₁₅ is independently selected from thegroup consisting of halogens, alkyl groups, substituted alkyl groups,alkoxy groups, substituted alkoxy groups, aryl groups, and substitutedaryl groups. The structure of Formula (AD) is

In the structure of Formula (AD), the variable g is zero or a positiveinteger from 1 to 6, and each R₂₀ is independently selected from thegroup consisting of halogens, alkyl groups, substituted alkyl groups,alkoxy groups, substituted alkoxy groups, aryl groups, and substitutedaryl groups. The structure of Formula (AE) is

In the structure of Formula (AE), the variable j is zero or a positiveinteger from 1 to 4, and each R₂₅ is independently selected from thegroup consisting of halogens, alkyl groups, substituted alkyl groups,alkoxy groups, substituted alkoxy groups, aryl groups, and substitutedaryl groups. The structure of Formula (AF) is

In the structure of Formula (AF), the variable X₁, X₂, X₃, X₄, and X₅are independently selected from the group consisting of a carbon atomand a nitrogen atom, provided at least one and no more than three of X₁,X₂, X₃, X₄, and X₅ are nitrogen atoms; t is zero or a positive integerequal to 5−X where X is the number of nitrogen atoms; and each R₂₇ isindependently selected from the group consisting of halogens, alkylgroups, substituted alkyl groups, alkoxy groups, substituted alkoxygroups, aryl groups, and substituted aryl groups. The structure ofFormula (AG) is

In the structure of Formula (AG), the variable X₆ is selected from thegroup consisting of a carbon atom, an oxygen atom, a sulfur atom, and asecondary amine group, X₇, X₈, and X₉ are independently selected fromthe group consisting of a carbon atom and a nitrogen atom, at least oneand no more than three of X₆, X₇, X₈, and X₉ are non-carbon atoms; u iszero or a positive integer equal to 4−Y where Y is the number ofnon-carbon atoms in the ring structure; and each R₂₉ is independentlyselected from the group consisting of halogens, cyano groups, alkylgroups, substituted alkyl groups, alkoxy groups, substituted alkoxygroups, aryl groups, and substituted aryl groups.

When L is a trivalent linking group, v is 1, and R₂ can be selected fromthe group consisting of moieties conforming to the structure of one ofFormula (AH)-(AJ) below. The structure of Formula (AH) is

In the structure of Formula (AH), the variable k is zero or a positiveinteger from 1 to 8, and each R₃₀ is independently selected from thegroup consisting of halogens, alkyl groups, substituted alkyl groups,alkoxy groups, substituted alkoxy groups, aryl groups, and substitutedaryl groups. The structure of Formula (AI) is

In the structure of Formula (AI), the variable m is zero or a positiveinteger from 1 to 4, and each R₃₅ is independently selected from thegroup consisting of halogens, alkyl groups, substituted alkyl groups,alkoxy groups, substituted alkoxy groups, aryl groups, and substitutedaryl groups. The structure of Formula (AJ) is

In the structure of Formula (AJ), the variable p is zero or a positiveinteger from 1 to 3, p′ is zero or a positive integer from 1 to 3, andeach R₄₀ and R₄₅ is independently selected from the group consisting ofhalogens, alkyl groups, substituted alkyl groups, alkoxy groups,substituted alkoxy groups, aryl groups, and substituted aryl groups.

When L is a divalent liking group, v is 2, and R₂ can selected from thegroup consisting of moieties conforming to the structure of Formula (BA)below

In the structure of Formula (BA), the variable q is zero or a positiveinteger from 1 to 4, r is zero or a positive integer from 1 to 4, andeach R₅₀ and R₅₅ is independently selected from the group consisting ofhalogens, alkyl groups, substituted alkyl groups, alkoxy groups,substituted alkoxy groups, aryl groups, and substituted aryl groups.

When L is a divalent linking group, v is 3, and R₂ can be selected fromthe group consisting of moieties conforming to the structure of Formula(CA) below

In the structure of Formula (CA), the variable s is zero or a positiveinteger from 1 to 3, and each R₆₀ is independently selected from thegroup consisting of halogens, alkyl groups, substituted alkyl groups,alkoxy groups, substituted alkoxy groups, aryl groups, and substitutedaryl groups.

In a series of preferred embodiments, L is a divalent linking group, vis 1, and R₂ is a moiety conforming to the structure of Formula (AA).Within this series of preferred embodiments, the variable d preferablyis zero or 1. If d is 1, the group R₁₀ preferably is attached to thearyl ring in the para position relative to the bond to the linking groupL. Further if d is 1, the group R₁₀ preferably is a halogen (e.g.,bromine), an alkoxy group (e.g., a methoxy group), or an aryl group(e.g., a phenyl group).

In a series of preferred embodiments, L is a divalent linking group, vis 1, and R₂ is a moiety conforming to the structure of Formula (AC).Within this series of preferred embodiments, the variable d preferablyis zero or 1, with zero being particularly preferred.

As noted above, M₁ is a metal cation. Suitable metal cations include,but are not limited to, alkali metal cations (e.g., sodium), alkalineearth metal cations (e.g., calcium), transition metal cations (e.g.,zinc), and group 13 metal cations (e.g., aluminum). As utilized herein,the term “transition metal” is used to refer those elements in thed-block of the periodic table of elements, which corresponds to groups 3to 12 on the periodic table of elements. In a preferred embodiment, M₁is a metal cation selected from the group consisting of lithium, sodium,magnesium, aluminum, potassium, calcium, and zinc. In another preferredembodiment, M₁ is a lithium cation. In those embodiments in which thecompound contains more than one metal cation M₁, each M₁ can be the sameor different.

In a series of preferred embodiments, the nucleating agent can comprisea compound conforming to the structure of one of Formulae (IA)-(IM)below

The composition can comprise one or more metal salt compounds conformingto the structure of Formula (I). For example, the composition cancomprise any suitable combination of the compounds conforming to thestructures of (IA)-(IM) depicted above. More specifically, thecomposition can comprise a compound conforming to the structure ofFormula (IA) and compound conforming to the structure of Formula (IL).In another specific embodiment, the composition can comprise a compoundconforming to the structure of Formula (IB) and a compound conforming tothe structure of Formula (IL). In yet another specific embodiment, thecomposition can comprise a compound conforming to the structure ofFormula (IC) and a compound conforming to the structure of Formula (IL).Blends of these compounds can be used to produce compositions thatexhibit a desired combination of properties, with one compound providingone benefit and another compound providing an additional benefit.

The metal salt compounds of Formula (I) and the more specific structuresencompassed by Formula (I) can be synthesized using any suitabletechnique, many of which will be readily apparent to those of ordinaryskill in the art. For example, if the acid used in making the compoundis commercially available, the compound can be prepared by reacting theacid with a suitable base (e.g., a base comprising the desired metalcation and a Brønsted base) in a suitable medium (e.g., an aqueousmedium). If the acid to be used in making the metal salt compound is notcommercially available, the acid can be synthesized, for example, usingany of the techniques illustrated below in the examples. Once thedesired acid is obtained, the compound can be produced as describedabove (e.g., by reacting the acid with a suitable base in an appropriatemedium).

The metal salt compounds of Formula (I) and the more specific structuresencompassed by Formula (I) can be produced in various particle shapesand sizes. In general, these salt compounds form layered crystallinestructures wherein the metal ions are present in galleries which aresandwiched between alternating layers of organic surfaces. As a result,flat platelet-like particles are often produced wherein the nucleatingsurfaces are exposed on the top and bottom of the particles, rather thanthe edges. The aspect ratio of these platelet-like particles istypically defined as the diameter, or breadth, versus the thickness.Elongated platelets, or “lath-like” crystals, are another particlemorphology possible with these metal salt compounds. In these elongatedstructures, the aspect ratio typically is defined as the ratio of thelength to the width. Aspect ratios of 2:1 up through 50:1 are possible.Particles with aspect ratios can align in molten polymer flow fieldssuch that the flat surfaces are parallel to the machine, or flow,direction and parallel to the transverse, or cross, direction. As aresult, the nucleating surfaces are exposed only in the normal directionof the polymer melt during part fabrication (exceptions would resultwhen platelet-shaped particles possessed an aspect ratio insufficientfor flat registry, and tumbling in the polymer flow direction results).Preferred particle orientations, or “registry”, combined with specificcrystallographic interactions with polyethylene during the nucleationevent, can create directed lamellar growth which can result in uniqueand beneficial orientations of polyethylene crystals within the articlesproduced.

The particles of the nucleating agent discussed above can have anysuitable size. Preferably, the particles of the nucleating agent aresmall enough that they are not visible in a finished article made fromthe thermoplastic polymer composition. Thus, in a preferred embodiment,the particles of the nucleating agent preferably are less than 25microns in diameter, more preferably less than 20 microns in diameter,and most preferably less than 15 microns in diameter.

The nucleating agent can be present in the thermoplastic polymercomposition in any suitable amount. The nucleating agent can be presentin the thermoplastic polymer composition in an amount of about 50 partsper million (ppm) or more, about 100 ppm or more, about 250 ppm or more,or about 500 ppm or more, based on the total weight of the thermoplasticpolymer composition. The nucleating agent typically is present in thethermoplastic polymer composition in an amount of about 10,000 ppm orless, about 7,500 ppm or less, about 5,000 ppm or less, about 4,000 ppmor less, or about 3,000 ppm or less, based on the total weight of thethermoplastic polymer composition. Thus, in certain embodiments of thethermoplastic polymer composition, the nucleating agent is present inthe thermoplastic polymer composition in an amount of about 50 to about10,000 ppm, about 100 to about 7,500 ppm (e.g., about 100 to about 5,000ppm), about 250 to about 5,000 ppm (e.g., about 250 to about 4,000 ppmor about 250 to about 3,000 ppm), or about 500 to about 5,000 ppm (e.g.,about 500 to about 4,000 ppm or about 500 to about 3,000 ppm), based onthe total weight of the polymer composition.

The thermoplastic polymer composition of the invention can also beprovided in the form of a masterbatch composition designed for additionor let-down into a virgin thermoplastic polymer. In such an embodiment,the thermoplastic polymer composition will generally contain a higheramount of the nucleating agent as compared to a thermoplastic polymercomposition intended for use in the formation of an article ofmanufacture without further dilution or addition to a virginthermoplastic polymer. For example, the nucleating agent can be presentin such a thermoplastic polymer composition in an amount of about 1 wt.% to about 10 wt. % (e.g., about 1 wt. % to about 5 wt. % or about 2 wt.% to about 4 wt. %), based on the total weight of the thermoplasticpolymer composition.

The thermoplastic polymer composition of the invention can contain otherpolymer additives in addition to the aforementioned nucleating agent.Suitable additional polymer additives include, but are not limited to,antioxidants (e.g., phenolic antioxidants, phosphite antioxidants, andcombinations thereof), anti-blocking agents (e.g., amorphous silica anddiatomaceous earth), pigments (e.g., organic pigments and inorganicpigments) and other colorants (e.g., dyes and polymeric colorants),fillers and reinforcing agents (e.g., glass, glass fibers, talc, calciumcarbonate, and magnesium oxysulfate whiskers), nucleating agents,clarifying agents, acid scavengers (e.g., metal salts of fatty acids,such as the metal salts of stearic acid, and dihydrotalcite), polymerprocessing additives (e.g., fluoropolymer polymer processing additives),polymer cross-linking agents, slip agents (e.g., fatty acid amidecompounds derived from the reaction between a fatty acid and ammonia oran amine-containing compound), fatty acid ester compounds (e.g., fattyacid ester compounds derived from the reaction between a fatty acid anda hydroxyl-containing compound, such as glycerol, diglycerol, andcombinations thereof), and combinations of the foregoing.

As noted above, the thermoplastic polymer composition of the inventioncan contain other nucleating agents in addition to those compoundsconforming to the structure of Formula (I). Suitable nucleating agentsinclude, but are not limited to,2,2′-methylene-bis-(4,6-di-tert-butylphenyl)phosphate salts (e.g.,sodium 2,2′-methylene-bis-(4,6-di-tert-butylphenyl)phosphate or aluminum2,2′-methylene-bis-(4,6-di-tert-butylphenyl)phosphate),bicyclo[2.2.1]heptane-2,3-dicarboxylate salts (e.g., disodiumbicyclo[2.2.1]heptane-2,3-dicarboxylate or calciumbicyclo[2.2.1]heptane-2,3-dicarboxylate), cyclohexane-1,2-dicarboxylatesalts (e.g., calcium cyclohexane-1,2-dicarboxylate, monobasic aluminumcyclohexane-1,2-dicarboxylate, dilithium cyclohexane-1,2-dicarboxylate,or strontium cyclohexane-1,2-dicarboxylate), glycerolate salts (e.g.,zinc glycerolate), phthalate salts (e.g., calcium phthalate),phenylphosphonic acid salts (e.g., calcium phenylphosphonate), andcombinations thereof. For the bicyclo[2.2.1]heptane-2,3-dicarboxylatesalts and the cyclohexane-1,2-dicarboxylate salts, the carboxylatemoieties can be arranged in either the cis- or trans-configuration, withthe cis-configuration being preferred.

As noted above, the thermoplastic polymer composition of the inventioncan also contain a clarifying agent. Suitable clarifying agents include,but are not limited to, trisamides and acetal compounds that are thecondensation product of a polyhydric alcohol and an aromatic aldehyde.Suitable trisamide clarifying agents include, but are not limited to,amide derivatives of benzene-1,3,5-tricarboxylic acid, derivatives ofN-(3,5-bis-formylamino-phenyl)-formamide (e.g.,N-[3,5-bis-(2,2-dimethyl-propionylamino)-phenyl]-2,2-dimethyl-propionamide),derivatives of 2-carbamoyl-malonamide (e.g.,N,N′-bis-(2-methyl-cyclohexyl)-2-(2-methyl-cyclohexylcarbamoyl)-malonamide),and combinations thereof. As noted above, the clarifying agent can be anacetal compound that is the condensation product of a polyhydric alcoholand an aromatic aldehyde. Suitable polyhydric alcohols include acyclicpolyols such as xylitol and sorbitol, as well as acyclic deoxy polyols(e.g., 1,2,3-trideoxynonitol or 1,2,3-trideoxynon-1-enitol). Suitablearomatic aldehydes typically contain a single aldehyde group with theremaining positions on the aromatic ring being either unsubstituted orsubstituted. Accordingly, suitable aromatic aldehydes includebenzaldehyde and substituted benzaldehydes (e.g.,3,4-dimethyl-benzaldehyde or 4-propyl-benzaldehyde). The acetal compoundproduced by the aforementioned reaction can be a mono-acetal, di-acetal,or tri-acetal compound (i.e., a compound containing one, two, or threeacetal groups, respectively), with the di-acetal compounds beingpreferred. Suitable acetal-based clarifying agents include, but are notlimited to, the clarifying agents disclosed in U.S. Pat. Nos. 5,049,605;7,157,510; and 7,262,236.

The thermoplastic polymer composition of the invention can be producedby any suitable method or process. For example, the thermoplasticpolymer composition can be produced by simple mixing of the individualcomponents of the thermoplastic polymer composition (e.g., thermoplasticpolymer, nucleating agent, and other additives, if any). Thethermoplastic polymer composition can also be produced by mixing theindividual components under high shear or high intensity mixingconditions. The thermoplastic polymer composition of the invention canbe provided in any form suitable for use in further processing toproduce an article of manufacture from the thermoplastic polymercomposition. For example, the thermoplastic polymer compositions can beprovided in the form of a powder (e.g., free-flowing powder), flake,pellet, prill, tablet, agglomerate, and the like.

The thermoplastic polymer composition of the invention is believed to beuseful in producing thermoplastic polymer articles of manufacture. Thethermoplastic polymer composition of the invention can be formed into adesired thermoplastic polymer article of manufacture by any suitabletechnique, such as injection molding (e.g., thin-wall injection molding,multicomponent molding, overmolding, or 2K molding), blow molding (e.g.,extrusion blow molding, injection blow molding, or injection stretchblow molding), extrusion (e.g., fiber extrusion, tape (e.g., slit tape)extrusion, sheet extrusion, film extrusion, cast film extrusion, pipeextrusion, extrusion coating, or foam extrusion), thermoforming,rotomolding, film blowing (blown film), film casting (cast film),compression molding, extrusion compression molding, extrusioncompression blow molding, and the like. Thermoplastic polymer articlesmade using the thermoplastic polymer composition of the invention can becomprised of multiple layers (e.g., multilayer blown or cast films ormultilayer injection molded articles), with one or any suitable numberof the multiple layers containing a thermoplastic polymer composition ofthe invention.

The thermoplastic polymer composition of the invention can be used toproduce any suitable article of manufacture. Suitable articles ofmanufacture include, but are not limited to, medical devices (e.g.,pre-filled syringes for retort applications, intravenous supplycontainers, and blood collection apparatus), food packaging, liquidcontainers (e.g., containers for drinks, medications, personal carecompositions, shampoos, and the like), apparel cases, microwavablearticles, shelving, cabinet doors, mechanical parts, automobile parts,sheets, pipes, tubes, rotationally molded parts, blow molded parts,films, fibers, and the like.

The addition of the heterogeneous nucleating agents described above hasconsistently been demonstrated to nucleate the thermoplastic polymer(e.g., polyolefin, such as polyethylene), as observed, for example,through an increase in the peak polymer recrystallization temperature ofthe polymer. Further, the addition of the nucleating agent has beenobserved to favorably improve certain physical properties of thethermoplastic polymer, such as the haze, tear strength (either absolutetear strength or the balance between tear strength in the machine andtransverse directions), stiffness, and barrier properties. When thethermoplastic polymer composition is used to produce an article, thephysical property effects of the nucleating agent on the polymer can beimproved by manipulating the characteristic process time (T) and/orselecting a polymer exhibiting an appropriate average relaxation time(λ). In this context, the characteristic process time (T) is the timeduring which the molten polymer is subjected to strain, which results instress (e.g., extensional melt stress) in the polymer melt. The averagerelaxation time (λ) is a characteristic of the polymer and is a measureof the time it takes the polymer melt to relieve stress. The averagerelaxation time (λ) is dependent upon, inter alia, the molecular weightof the polymer, the molecular weight distribution of the polymer, andthe degree of branching in the polymer. For example, it is known that λis proportional to the molecular weight of the polymer, with highermolecular weights leading to longer relaxation times. Further, mostcommercial polyolefins are more or less polydisperse, with the degree ofpolydispersity typically indicated by Mw/Mn as determined by GPC. Thispolydispersity inherently yields a series of molecular weight-dependentrelaxation times, though many techniques can only measure a singleaverage relaxation time for such polydisperse systems. Thepolydispersity of the polymer, and the series of molecularweight-dependent relaxation times and/or average relaxation time, can beintentionally further broadened or manipulated by making bimodal blends,as described above.

Many thermoplastic polymers, such as polyethylene, crystallize by chainfolding, producing crystalline lamellae interspersed with an amorphousphase. In processes in which the molten polymer is subject to relativelylittle strain, the polymer chains in the polymer melt are not wellaligned and the polymer melt (e.g., polyethylene melt) cools untilsufficient chain alignment occurs to spontaneously initiate crystallinelamellae growth. When this spontaneous lamellae growth occurs, thenucleation density is relatively low, and the growing lamellae travelfurther before impinging on each other. This allows the lamellae tobegin to change their direction or splay out, with the extreme ofsplaying being the formation of full spherulites. Because of therelatively long time it takes for self-nucleation to occur under theseconditions, a nucleating agent (such as that described in thisapplication) added to the polymer melt will have the opportunity tocontrol a larger proportion of the lamellae growth. And with a largerproportion of the lamellae being formed by the nucleating agent, thenucleating agent will effectively influence the physical properties ofthe polymer and article.

Certain processes, such as film blowing, can impart significantextensional strain to the polymer melt in the machine direction (i.e.,the direction in which the molten polymer exits the die). The resultingstress causes polymer chains to uncoil from their entropic random coil,resulting in extended polymer chain alignments in the machine direction.If this orientation persists as the polymer melt cools, some of thesealigned, extended chain segments can crystallize from the melt to formrelatively long fibrils. The fibrils are very effective in nucleatingchain-folding lamellae growth. The lamellae form and begin to growperpendicular to the fibril axis and more or less radially around thefibrils. Since the nucleation density is higher, growing lamellae mayimpinge on each other before significant splaying begins. This processis referred to herein as “stress-induced fibril self-nucleation.” Undercertain conditions as described below, this stress-induced fibrilself-nucleation can become prominent in the polymer (e.g., apolyethylene polymer). Thus, any heterogeneous nucleating agent mustcompete with this stress-induced fibril self-nucleation, making thenucleating agent less effective at favorably influencing the physicalproperties of the polymer and the article. The effects of λ and T onstress-induced fibril self-nucleation and the effectiveness ofnucleating agents are described below.

Assuming a constant T, a shorter λ means that more stress relaxationoccurs and less polymer chain orientation (e.g., polymer chainorientation induced by the extensional strain on the polymer melt)remains at the end of T. Under such conditions, stress-induced fibrilself-nucleation will be less prominent in the polymer, and a nucleatingagent will be more effective at controlling lamellae growth andinfluencing the physical properties of the polymer and the article. Atthe same T, a longer λ means that less stress relaxation occurs and morepolymer chain orientation remains at the end of T. Under this set ofconditions, stress-induced fibril self-nucleation will be more prominentin the polymer, and a nucleating agent will be less effective atcontrolling lamellae growth and influencing the physical properties ofthe polymer and the article.

In assessing the effects of λ and T on stress-induced fibrilself-nucleation and the effectiveness of heterogeneous nucleating agents(such as those described herein) in, for example, blown film processes,it can be instructive to consider the ratio of λ to T (λ/T), which willbe referred to hereinafter as the “Fabrication Time Ratio” (FTR). TheFTR is of the same form as and roughly analogous to the Deborah number(De). As illustrated by the foregoing discussion, a lower FTR means thatless stress-induced fibril self-nucleation will occur in the polymer,making a nucleating agent more effective at influencing the physicalproperties. And a higher FTR means that more stress-induced fibrilself-nucleation will occur in the polymer, making a nucleating agentless effective at influencing the physical properties. Since the processtimes of most commercial processes can only be varied within arelatively narrow window, the more viable option for changing the FTR toimprove or optimize the effect of the nucleating agent is to change λ,which is done by varying the polymer properties. More specifically, fora given process, the effect of the nucleating agent can be optimized toachieve the desired result by varying the polymer properties and λ tobetter match the process time T.

Thus, if one is unable to achieve the desired degree of nucleationeffects (e.g., improved barrier properties or increased tear strength)using a given nucleating agent and polymer in a process, one can improvethe results by selecting a different polymer having a shorter λ. Forexample, one can select a bimodal polymer containing a first fractionhaving a relatively low Melt Index (which is typically indicative of ahigher molecular weight and therefore a longer λ) and a second fractionhaving a relatively high Melt Index (which is typically indicative of alower molecular weight and therefore a shorter λ). In this system, thehigher Melt Index fraction may provide a λ for the entire polymer thatresults in less stress-induced fibril self-nucleation and improvedresponse to the heterogeneous nucleating agent. Alternatively, thenucleating agent may only nucleate the higher Melt Index fraction (dueto the shorter λ exhibited by the fraction), leaving the lower MeltIndex fraction to undergo stress-induced fibril self-nucleation inbasically the same manner as if no nucleating agent were present.Regardless of the mechanism at work, the end result is that thenucleating agent controls more lamellae growth in the polymer and exertsan increased influence on the physical properties of the polymer. Whilethe foregoing example describes the use of bimodal polymers, the sameeffects can be achieved using multimodal polymers and physical blends ofdistinct polymers because each of these alternatives also provides ameans to reduce λ. Further, similar improvements can be achieved byselecting a polymer having a narrower molecular weight distribution (asindicated by a lower melt flow ratio). A narrower molecular weightdistribution typically indicates the absence of a higher molecularweight “tail” or fraction in the polymer that might increase λ for thepolymer. Also, similar improvements can be achieved by selecting apolymer having less long chain branching, since long chain branching canresult in melt entanglement that can increase λ.

In a second embodiment, the invention provides a compound conforming tothe structure of Formula (C)

In the structure of Formula (C), R₁₀₁ is selected from the groupconsisting of a cyclopentyl group and moieties conforming to thestructure of Formula (CI). The structure of Formula (CI) is

In the structure of (CI), R₁₀₅ is selected from the group consisting ofhydrogen and halogens. The variable x is a positive integer; each M₁ isa metal cation; y is the valence of the cation; and z is a positiveinteger. The variable b is zero or a positive integer. When b is apositive integer, each Q₁ is a negatively-charged counterion and a isthe valence of the negatively-charged counterion. The values of x, y, z,a, and b satisfy the equation x+(ab)=yz.

M₁ can be any of the cations described above as being suitable for thecompound conforming to the structure of Formula (I), including thosecations noted as being preferred for the structure of Formula (I). In apreferred embodiment, M₁ is a cation of a metal selected from the groupconsisting of alkali metals and alkaline earth metals. In anotherpreferred embodiment, M₁ is a cation of a metal selected from the groupconsisting of alkali metals. In a preferred embodiment, M₁ is a lithiumcation. Q₁, if present, can be any of the anions described above asbeing suitable for the compound conforming to the structure of Formula(I), including those anions noted as being preferred for the structureof Formula (I).

In a preferred embodiment, R₁₀₁ is a cyclopentyl group. The cyclopentylgroup can be unsubstituted or substituted. The substituted cyclopentylgroup can conform to the structure of Formula (AC) above. Preferably,the cyclopentyl group is unsubstituted. In a more specific embodiment,R₁₀₁ is a cyclopentyl group, the variable x is 1, M₁ is a lithiumcation, y is 1, z is 1, and b is zero.

In another preferred embodiment, R₁₀₁ is a moiety conforming to thestructure of Formula (CI). In a more specific embodiment, R₁₀₁ is amoiety conforming to the structure of Formula (CI), and R₁₀₅ ishydrogen. In another specific embodiment, R₁₀₁ is a moiety conforming tothe structure of Formula (CI), R₁₀₅ is hydrogen, x is 1, M₁ is a lithiumcation, y is 1, z is 1, and b is zero. In another specific embodiment,R₁₀₁ is a moiety conforming to the structure of Formula (CI), and R₁₀₅is a halogen, preferably bromine. In a more specific embodiment, R₁₀₁ isa moiety conforming to the structure of Formula (CI), R₁₀₅ is bromine, xis 1, M₁ is a lithium cation, y is 1, z is 1, and b is zero.

In a series of additional embodiments, the compound of this secondembodiment can be used as a nucleating agent for a thermoplastic polymeras described above in the first embodiment of the invention. Inparticular, these additional embodiments include thermoplastic polymercompositions comprising a thermoplastic polymer, preferably a polyolefinpolymer (e.g., a polyethylene polymer), and one or more of the specificcompounds described in the preceding paragraphs.

In a third embodiment, the invention provides a compound conforming tothe structure of Formula (CX)

In the structure of (CX), R₁₁₁ is selected from the group consisting ofa cyclopentyl group and moieties conforming to the structure of Formula(CXI); and R₁₁₂ is selected from the group consisting of hydrogen andhydroxy. The structure of Formula (CXI) is

In the structure of (CXI), R₁₁₅ is selected from the group consisting ofhydrogen, a halogen, methoxy, and phenyl. The variable x is a positiveinteger; each M₁ is a metal cation; y is the valence of the cation; andz is a positive integer. The variable b is zero or a positive integer.When b is a positive integer, each Q₁ is a negatively-charged counterionand a is the valence of the negatively-charged counterion. The values ofx, y, z, a, and b satisfy the equation x+(ab)=yz. Further, if R₁₁₅ ishydrogen, then R₁₁₂ is hydrogen, x is 1, M₁ is a lithium cation, y is 1,z is 1, and b is zero. Also, if R₁₁₅ is a methoxy group, then R₁₁₂ is ahydroxy group.

M₁ can be any of the cations described above as being suitable for thecompound conforming to the structure of Formula (I), including thosecations noted as being preferred for the structure of Formula (I). In apreferred embodiment, M₁ is a cation of a metal selected from the groupconsisting of alkali metals and alkaline earth metals. In anotherpreferred embodiment, M₁ is a cation of a metal selected from the groupconsisting of alkali metals. In a preferred embodiment, M₁ is a lithiumcation. Q₁, if present, can be any of the anions described above asbeing suitable for the compound conforming to the structure of Formula(I), including those anions noted as being preferred for the structureof Formula (I).

In a preferred embodiment, R₁₁₁ is a cyclopentyl group. The cyclopentylgroup can be unsubstituted or substituted. The substituted cyclopentylgroup can conform to the structure of Formula (AC) above. Preferably,the cyclopentyl group is unsubstituted. In a more specific embodiment,R₁₁₁ is a cyclopentyl group, the variable x is 1, M₁ is a lithiumcation, y is 1, z is 1, and b is zero.

In another preferred embodiment, R₁₁₁ is a moiety conforming to thestructure of Formula (CXI). In a more specific embodiment, R₁₁₁ is amoiety conforming to the structure of Formula (CXI), and R₁₁₅ ishydrogen. In another more specific embodiment, R₁₁₁ is a moietyconforming to the structure of Formula (CXI), and R₁₁₅ is a methoxygroup. In yet another specific embodiment, R₁₁₁ is a moiety conformingto the structure of Formula (CXI), R₁₁₅ is a methoxy group, x is 1, M₁is a lithium cation, y is 1, z is 1, and b is zero. In another morespecific embodiment, R₁₁₁ is a moiety conforming to the structure ofFormula (CXI), and R₁₁₅ is a halogen, preferably chlorine. In a yet morespecific embodiment, R₁₁₁ is a moiety conforming to the structure ofFormula (CXI), R₁₁₅ is a halogen, preferably chlorine, and R₁₁₂ ishydrogen. In another more specific embodiment, R₁₁₁ is a moietyconforming to the structure of Formula (CXI), R₁₁₅ is chlorine, R₁₁₂ ishydrogen, and M₁ a cation of a metal selected from the group consistingof alkali metals, preferably sodium. In a more specific embodiment, R₁₁₁is a moiety conforming to the structure of Formula (CXI), R₁₁₅ ischlorine, R₁₁₂ is hydrogen, x is 1, M₁ a sodium cation, y is 1, z is 1,and b is zero.

In a series of additional embodiments, the compound of this thirdembodiment can be used as a nucleating agent for a thermoplastic polymeras described above in the first embodiment of the invention. Inparticular, these additional embodiments include thermoplastic polymercompositions comprising a thermoplastic polymer, preferably a polyolefinpolymer (e.g., a polyethylene polymer), and one or more of the specificcompounds described in the preceding paragraphs.

In a fourth embodiment, the invention provides a compound conforming tothe structure of Formula (CXX)

In the structure of (CXX), the variable x is a positive integer. Each M₁is a cation of a metal selected from the group consisting of alkalimetals, alkaline earth metals, and zinc; y is the valence of the cation;and z is a positive integer. The variable b is zero or a positiveinteger. When b is a positive integer, each Q₁ is a negatively-chargedcounterion and a is the valence of the negatively-charged counterion.The values of x, y, z, a, and b satisfy the equation x+(ab)=yz.

In a preferred embodiment, M₁ is a cation of a metal selected from thegroup consisting of alkali metals and alkaline earth metals. In anotherpreferred embodiment, M₁ is a cation of a metal selected from the groupconsisting of alkali metals. In a more specific embodiment, M₁ is alithium cation. In another specific embodiment, x is 1, M₁ is a lithiumcation, y is 1, z is 1, and b is zero.

In a series of additional embodiments, the compound of this fourthembodiment can be used as a nucleating agent for a thermoplastic polymeras described above in the first embodiment of the invention. Inparticular, these additional embodiments include thermoplastic polymercompositions comprising a thermoplastic polymer, preferably a polyolefinpolymer (e.g., a polyethylene polymer), and one or more of the specificcompounds described in the preceding paragraphs.

In another embodiment, the invention provides an additive compositioncomprising a nucleating agent as described above and an acid scavengercompound. The nucleating agent present in the composition can be any oneor more of the nucleating agent compounds described above, such as acompound conforming to the structure of Formula (I), a compoundconforming to the structure of Formula (C), a compound conforming to thestructure of Formula (CX), a compound conforming to the structure ofFormula (CXX), or any suitable mixture of such compounds. Preferably,the nucleating agent in the additive composition is selected from thegroup consisting of compounds conforming to the structure of Formula(CX). More preferably, the nucleating agent is a compound conforming tothe structure of Formula (CX) in which R₁₁₂ is hydrogen, R₁₁₁ is amoiety conforming to the structure of Formula (CXI), and R₁₁₅ is ahalogen. In a more specific preferred embodiment, the nucleating agentis a compound conforming to the structure of Formula (CX) in which R₁₁₂is hydrogen, R₁₁₁ is a moiety conforming to the structure of Formula(CXI), R₁₁₅ is chlorine, M₁ is a sodium cation, x is 1, y is 1, z is 1,and b is 0.

Preferably, the acid scavenger is selected from the group consisting ofmetal salts of fatty acids and synthetic hydrotalcite compounds.Suitable metal salts of fatty acids include, but are not limited to, themetal salts of C₁₂-C₂₂ fatty acids, such as stearic acid. In a preferredembodiment, the acid scavenger is selected from the group consisting ofthe zinc, potassium, and lanthanum salts of stearic acid. Suitablesynthetic hydrotalcite compounds include, but are not limited to, DHT-4Aacid scavenger sold by Kyowa Chemical Industry Co., Ltd.

The nucleating agent and the acid scavenger can be present in theadditive composition in any suitable amounts. For example, thenucleating agent and the acid scavenger can be present in the additivecomposition in a ratio (nucleating agent to acid scavenger) of about10:1 to about 1:10 based on the weight of the nucleating agent and theacid scavenger in the composition. More preferably, the nucleating agentand the acid scavenger are present in the additive composition in aratio (nucleating agent to acid scavenger) of about 4:1 to about 1:4,about 3:1 to about 1:3, about 1:1 to about 1:4, or about 1:1 to about1:3 based on the weight of the nucleating agent and the acid scavengerin the additive composition.

Surprisingly, it has been found that the nucleating agent and the acidscavenger synergistically interact when the additive compositiondescribed above is added to a thermoplastic polymer. In particular, ithas been found that the addition of the acid scavenger can improve theperformance of the nucleating agent. For example, the addition of boththe nucleating agent and the acid scavenger can improve the physicalproperty enhancements to the polymer beyond those realized when thenucleating agent alone is used. Also, the addition of the acid scavengercan permit one to achieve a desired level of physical propertyenhancements to the polymer using less nucleating agent than would berequired if the nucleating agent were added alone. This synergy isconsidered especially surprising given the fact that the acid scavengerhas not been observed to nucleate the polymer itself. For example, theaddition of the acid scavenger alone does not have an appreciable effecton the physical properties of the polymer.

The additive composition described above is intended for incorporationinto a thermoplastic polymer, such as the polyethylene and polypropylenepolymers described earlier in this application. In particular, it isbelieved that the additive composition is particularly effective whenused in a high density polyethylene polymer. In these polymers, theaddition of the additive composition has been observed to significantlylower the machine direction shrinkage, which is indicative of increasedmachine direction orientation of the crystalline lamellae, andsignificantly improve the stiffness and heat deflection temperature ofthe polymer.

The following examples further illustrate the subject matter describedabove but, of course, should not be construed as in any way limiting thescope thereof.

Preparation Example EX1

This example demonstrates the preparation of 4-chlorocarbonyl-benzoicacid methyl ester having the following structure

In a 4 L kettle with mechanical stirrer, reflux condenser, additionfunnel, thermometer, water bath and hot plate, 438 g dimethylterephthalate (DMT) and 2700 mL toluene were added. The kettle washeated to about 65° C. to dissolve all the DMT. After dissolution, apotassium hydroxide solution (144.54 g in 700 mL methanol) was addeddropwise over 45 minutes. The reaction was stirred at 65° C. for threehours and then the reaction cooled to room temperature overnight. Thesolid was collected after filtration and washed with 3750 mL toluene at80° C. The product was filtered again and dried in the oven at 110° C.The yield was 465.9 g (95.3%).

In a 2 L three neck round bottom flask with mechanical stirrer, additionfunnel, water bath, thermometer, nitrogen sweep, and hot plate, 130.31 gof the product made in previous step and 1000 mL toluene were added.Then 48 mL of thionyl chloride was added dropwise. After the completionof addition, the mixture was heated to 67° C. for three hours. Thereaction cooled to room temperature and was stirred overnight. Thecontents were filtered to collect the filtrate. The excess solvent wasremoved by vacuum and 86.52 g of product was obtained (73% yield).

Preparation Example EX2

This example demonstrates the synthesis of N-cyclopentyl-terephthalamicacid having the following structure

A 2 L round bottom flask was charged with 15.44 g of sodium bicarbonate,15.75 g of cyclopentyl amine, 0.5 g of triethylamine, and 200 mL oftetrahydrofuran (THF). The flask was chilled in an ice bath, and then asolution of 4-chlorocarbonyl-benzoic acid methyl ester (36.78 g in about100 mL of THF) was added dropwise to the flask. After addition, themixture was heated to reflux. The reaction was monitored with infraredspectroscopy (IR) until the peak at 1780 cm⁻¹ disappeared. Then themixture was poured into about 2 L of water and stirred for approximately20 minutes. The solid product was collected after filtration and driedin the oven at 100° C.

To a 2 L three neck round bottom flask, 21 gram of the product made inthe previous step and 150 mL of methanol were added. The mixture washeated to reflux and potassium hydroxide (4.76 g, pre-dissolved inmethanol) was added. The reaction was monitored with IR until the peakat 1720 cm⁻¹ disappears. Then, 400 mL of water was added, and anyinsoluble impurities were filtered off. The pH of the filtrate wasadjusted to about 2 and a precipitate formed. The solid product wasfiltered and dried in an oven at 100° C.

Preparation Example EX3

This example demonstrates the production of the potassium salt ofN-cyclopentyl-terephthalamic acid having the following structure

In a beaker, 10 g of N-cyclopentyl-terephthalamic acid was added to 50mL H₂O. Then, 2.41 g of potassium hydroxide was dissolved in a separatebeaker with about 20 mL of H₂O. The potassium hydroxide solution wasadded into the N-cyclopentyl-terephthalamic acid slurry and most of thesolid dissolved. To remove any undissolved material, the mixture wasfiltered. The filtrate was collected and the water was evaporated off toyield the product. The product was dried overnight in an oven at 110° C.

Preparation Example EX4

This example demonstrates the production of N-phenyl-terephthalamic acidhaving the following structure

To a 1 L three neck round bottom flask with magnetic stirrer, additionfunnel, ice bath, nitrogen sweep, scrubber and hot plate, 93.13 g ofaniline, 42.30 g of sodium bicarbonate, 0.5 g of triethylamine, and 300mL of tetrahydrofuran (THF) were added. The mixture was cooled to below10° C. and then a solution of 100 g of 4-chlorocarbonyl-benzoic acidmethyl ester in 100 mL of tetrahydrofuran was added dropwise. Thetemperature was maintained at about 10° C. during addition. Afteraddition, the mixture was heated to reflux and monitored to completionof reaction by IR (disappearance of peak at 1780 cm⁻¹). Aftercompletion, the reaction was diluted to 2 L with cold deionized (DI)water and stirred for approximately 20 minutes. The solid product wasfiltered and dried in an oven at 110° C. After drying, 105.6 g ofproduct was obtained (82.2% yield).

In a 1 L Erlenmeyer flask with magnetic stir bar and stir plate, 15.94 gof the product made in previous step and 200 mL of methanol were added.Then, potassium hydroxide (3.87 g) that was pre-dissolved in methanolwas added. The reaction was monitored by IR (disappearance of the peakat about 1720 cm⁻¹). After completion, the reaction was diluted with 400mL water. Solid impurities were removed by filtration and the pH of thefiltration was adjusted to about 2. A product precipitated out at thisstep and was collected by filtration. The product was washed with moreDI water wash until neutral, and the product was dried in an oven at100° C. After drying, 14.47 g of the product was obtained (95% yield).

Preparation Example EX5

This example demonstrates the production of the lithium salt ofN-phenyl-terephthalamic acid having the following structure.

In a 500 mL Erlenmeyer flask with magnetic stir bar and stir plate, 13.3g of N-phenyl-terephthalamic acid and 200 mL of water were added. Themixture was heated to near boiling and then an aqueous solution oflithium hydroxide (containing 1.49 g of anhydrous lithium hydroxide) wasadded. The reaction was monitored by IR (disappearance of the peak at1677 cm⁻¹). After completion, the reaction was cooled down and filteredto collect the product. The product was dried in an oven at 110° C. and11.56 g of product was obtained.

Preparation Example EX6

This example demonstrates the production of4-(4-bromo-benzoylamino)benzoic acid having the following structure

In a 1 L three neck round bottom flask, 40 g of 4-aminobenzoic acid and400 mL of dioxane were added. The mixture was stirred until the aciddissolved. Then, 4-bromobenzoyl chloride solution (32.04 g in 100 mLdioxane) was added dropwise to the reaction. After addition, thereaction was stirred overnight and then filtered to collect the solid.The solid was washed with boiling water and then cold DI water until thepH was neutral. After drying, the product was obtained with 99.6% yield.

Preparation Example EX7

This example demonstrates the production of the potassium salt of4-(4-bromo-benzoylamino)benzoic acid having the following structure

In a beaker, 25 g of 4-(4-bromo-benzoylamino)benzoic acid and 200 mL ofDI water were added. The mixture was stirred until it formed a uniformslurry. Then, a potassium hydroxide solution (4.4 g in 100 mL water) wasadded. The reaction was stirred overnight, and the pH value dropped to10.6. The solid product was filtered and dried in an oven at 110° C.

Preparation Example EX8

This example demonstrates the production of the lithium salt of4-(4-bromo-benzoylamino)benzoic acid having the following structure

In a beaker, 3 grams of 4-(4-bromo-benzoylamino)benzoic acid wasdispersed into about 50 mL of water with stirring. Then a lithiumhydroxide monohydrate solution (0.39 g in 50 mL of H₂O) was added to theslurry. The reaction was stirred overnight and then the solid wascollected through filtration. The filtrate was washed with DI water andthen dried in an oven at 110° C.

Preparation Example EX9

This example demonstrates the production of the calcium salt of4-(4-bromo-benzoylamino)benzoic acid having the following structure

In a beaker, 3 grams of 4-(4-bromo-benzoylamino)benzoic acid wasdispersed into about 50 mL of water with stirring. Then, a calciumhydroxide solution (0.35 g in 50 mL water) was added to the slurry. Thereaction was stirred over the weekend and then filtered to collect theresulting solid. The filtrate was washed with DI water and then dried inan oven at 110° C.

Preparation Example EX10

This example demonstrates the production of4-(cyclopropanecarbonyl-amino)-benzoic acid having the followingstructure

In a three neck flask, 20.3 g of sodium carbonate was dispersed in 80 mLof THF under N₂. While stirring, 13.1 g of 4-aminibenzoic aciddispersion (in 15 mL of THF) and 10.0 g of cyclopropane carbonylchloride solution (in 15 mL of THF) were separately added dropwise. Thereaction was stirred overnight. Next, 10.15 g of sodium carbonate wasadded and the mixture was stirred for another 3 hours. Then, the THF wasevaporated and the reaction mixture was transferred to a 1 L beaker anddiluted with 600 mL of water. The pH was adjusted to about 2 withhydrochloric acid to form the product as a precipitate. The mixture wasfiltered to collect the precipitate, and the precipitate was dried in avacuum oven.

Preparation Example EX11

This example demonstrates the production of the lithium salt of4-(cyclopropanecarbonyl-amino)-benzoic acid having the followingstructure

In a beaker, 5 gram of 4-(cyclopropanecarbonyl-amino)-benzoic acid wasdispersed in 20 mL of water and then 1.13 g of lithium hydroxidemonohydrate was added. After a 20 minute stir, the reaction wasconcentrated in vacuo to obtain the product. The product was dried, andthe yield was about 2.59 g.

Preparation Example EX12

This example demonstrates the production of the sodium salt of4-(Cyclopropanecarbonyl-amino)-benzoic acid having the followingstructure

In a beaker, 20 gram of 4-(cyclopropanecarbonyl-amino)-benzoic acid wasmixed with 80 mL of water, and then 8.58 g of sodium hydroxide solution(50% in water) was added. After a 20 minute stir, the reaction wasconcentrated in vacuo to obtain the product.

Preparation Example EX13

This example demonstrates the production of the lithium salt of4-stilbenecarboxylic acid having the following structure

In a beaker, 1 gram of 4-stilbenecarboxylic acid (a mixture of trans andcis isomers) was dispersed in 25 mL of water. Then, 0.19 g of lithiumhydroxide monohydrate was dissolved in 25 mL of water and then added tothe acid suspension. The reaction was stirred overnight. The solidproduct was collected by filtration, washed three times with water, andthen dried in an oven at 110° C.

Preparation Example EX14

This example demonstrates the production of4-(1,3-Dioxo-octahydro-isoindol-2-yl)-2-hydroxy-benzoic acid having thefollowing structure

In a 500 mL four-neck round bottom flask equipped with temperatureprobe, heating mantle, agitator, and condenser, 21.20 g ofhexahydrophthalic anhydride and 50 mL of acetic acid were charged. At70° C., the mixture was stirred until uniform and then 21.7 g of4-aminosalicylic acid and 100 mL of acetic acid were charged. Afterheating to reflux for 6 hours, the contents were poured into ice cold DIH₂O and vacuum filtered to collect the solid. After washing with DI H₂Oand drying, 33.07 g of product were obtained.

Preparation Example EX15

This example demonstrates the production of the zinc salt of4-(1,3-dioxo-octahydro-isoindol-2-yl)-2-hydroxy-benzoic acid having thefollowing structure

In a beaker, 4-(1,3-dioxo-octahydro-isoindol-2-yl)-2-hydroxy-benzoicacid is suspended in about 100-150 mL of water with a magnetic stirrer.Then, a 25% solution of sodium hydroxide was slowly added until the pHstabilized at 12.5 and the solution became clear. Then, one equivalentof zinc chloride was added (used 1 eq instead of 0.5 because metal ionscan coordinate with the meta hydroxy group as well). The productsprecipitated out, and the mixture was filtered to collect the product.

Preparation Example EX16

This example demonstrates the production of4-(2,2-dimethyl-propionylamino)-benzoic acid having the followingstructure

In a three neck round bottom flask with overhead stirring, temperatureprobe, dry ice bath and reflux condenser, 25 g of 4-aminobenzoic acid,15.12 g of soda ash, and 200 mL of THF were added. Under stirring, 21.98g of pivaloyl chloride was added dropwise over 1-1.5 hour. Then, 22.68 gof soda ash was added, and the mixture was heated to 40° C. to drive thereaction to completion. The resulting mixture was diluted with 2 L of DIH₂O. The pH of the mixture was adjusted to 2.37 with concentratedhydrochloric acid, and then the mixture was filtered to collect theproduct.

Preparation Example EX17

This example demonstrates the production of the potassium salt of4-(2,2-Dimethyl-propionylamino)-benzoic acid having the followingstructure

In a beaker, 4-(2,2-dimethyl-propionylamino)-benzoic acid was suspendedin about 100-150 mL of water with a magnetic stirrer. Then, a 25%solution of potassium hydroxide was slowly added until the pH stabilizedat 12.5 and the solution became clear. The water was stripped off, andthe product was obtained.

Preparation Example EX18

This example demonstrates the production of the calcium salt of4-(2,2-Dimethyl-propionylamino)-benzoic acid having the followingstructure.

In a beaker, 4-(2,2-Dimethyl-propionylamino)-benzoic acid was suspendedin about 100-150 mL of water with a magnetic stirrer. Then, a 25%solution of potassium hydroxide was slowly added until the pH stabilizedat 12.5 and the solution became clear. Then, one equivalent of calciumchloride was added. The product precipitated out, and the mixture wasfiltered to collect the product.

Preparation Example EX19

This example demonstrates the production of N-4-methoxybenzoylaminosalicylic acid having the following structure

A three-neck round bottom flask was equipped with overhead stirring,temperature probe, dry ice bath, and reflux condenser. Then, 12.36 g of4-aminosalicylic acid, 16.75 g of soda ash, and 500 mL oftetrahydrofuran were charged into the flask. The mixture was cooledbelow 10° C. and then 14.85 g of 4-methoxybenzoyl chloride was addeddropwise over 1-1.5 hour. The resulting mixture was diluted with 2 L ofwater and filtered to collect the product.

Preparation Example EX20

This example demonstrates the production of N-4-methoxybenzoylaminosalicylic acid having the following structure

In a beaker, N-4-methoxybenzoyl aminosalicylic acid was suspended inabout 100-150 mL of water with a magnetic stirrer. Then, a 25% solutionof potassium hydroxide was slowly added until the pH stabilized at 12.5and the solution became clear. The water was stripped off and theproduct was obtained.

Preparation Example EX21

This example demonstrates the production of the lithium salt ofN-4-methoxybenzoyl aminosalicylic acid having the following structure

In a beaker, N-4-methoxybenzoyl aminosalicylic acid was suspended inabout 100-150 mL of water with a magnetic stirrer. Then, a 25% solutionof lithium hydroxide was slowly added until the pH stabilized at 12.5and the solution became clear. The water was stripped off and theproduct was obtained.

Preparation Example EX22

This example demonstrates the production of the sodium salt ofN-4-methoxybenzoyl aminosalicylic acid having the following structure

In a beaker, N-4-methoxybenzoyl aminosalicylic acid was suspended inabout 100-150 mL of water with a magnetic stirrer. Then, a 25% solutionof sodium hydroxide was slowly added until the pH stabilized at 12.5 andthe solution became clear. The water was stripped off and the productwas obtained.

Preparation Example EX23

This example demonstrates the production of4-(cyclobutanecarbonyl-amino)-benzoic acid having the followingstructure

In a flask, 20.3 g of sodium carbonate, 6.3 g of 4-aminobenzoic acid and80 mL of THF were added. Then, 5 g of cyclobutanecarbonyl chloride(diluted in 15 mL of THF) was added. The reaction was stirred undernitrogen over the weekend and the THF evaporated. The mixture wastransferred to a 1 L beaker and dissolved with 400 mL of water. Thesolution was acidified with hydrochloric acid until the pH was about 2and the product precipitated out. The product was collected byfiltration, then washed with water and dried.

Preparation Example EX24

This example demonstrates the production of the potassium salt of4-(cyclobutanecarbonyl-amino)-benzoic acid having the followingstructure

In a beaker, 4-(Cyclobutanecarbonyl-amino)-benzoic acid was suspended inapproximately 100-150 mL of water with a magnetic stir bar. Then, a 25%sodium hydroxide solution was added to raise the pH of the solution toabout 12.5. A clear solution was obtained, and then the water wasstripped away to collect the product as a powder.

Preparation Example EX25

This example demonstrates the production of4-(1,3-dioxo-1,3-dihydro-isoindol-2-yl)-benzoic acid having thefollowing structure

In a 500 mL four-neck round bottom flask equipped with a temperatureprobe, heating mantle, agitator, and condenser, 25.03 g of phthalicanhydride and 87 mL of acetic acid were charged. At 70° C., the reactionwas stirred until a clear solution was obtained. Then, 24.37 g of4-aminobenzoic acid was charged and the mixture was heated at reflux for2 hours. Then, 50 more mL of acetic acid was added. The contents werepoured into DI H₂O. The product was collected by filtration and thenwashed with DI H₂O. After drying, 43.345 g of product was obtained (96%yield).

Preparation Example EX26

This example demonstrates the production of the lithium salt of4-(1,3-dioxo-1,3-dihydro-isoindol-2-yl)-benzoic acid having thefollowing structure

In a 1000 mL beaker equipped with an agitator, 5.03 g of4-(1,3-Dioxo-1,3-dihydro-isoindol-2-yl)-benzoic acid and 100 mL of DIH₂O were charged. Lithium hydroxide was charged into the beaker and themixture stirred until all the acid was in solution. If the acid was notcompletely dissolved, lithium hydroxide in 0.1 g increments was addeduntil the acid fully dissolved. Rotary evaporation was used to recoverthe product.

Preparation Example EX27

This example demonstrates the production of the sodium salt of4-(1,3-Dioxo-1,3-dihydro-isoindol-2-yl)-benzoic acid having thefollowing structure

In a 1000 mL beaker equipped with an overhead agitator,4-(1,3-dioxo-1,3-dihydro-isoindol-2-yl)-benzoic acid and 100 mL of DIH₂O were added. The solution was stirred and a 25% sodium hydroxidesolution was slowly added until all the acid was in solution. The waterwas removed by rotary evaporation to recover the product.

Preparation Example EX28

This example demonstrates the production of N-cyclobutyl-terephthalamicacid methyl ester having the following structure

In a three-neck round bottom flask, 14.8 g of sodium carbonate and 50 mLof tetrahydrofuran were added. 5 g of cyclobutylamine was then added.Next, 11.59 g of 4-carbonylchloride methylbenzoate (diluted in 30 mL oftetrahydrofuran) was added dropwise. The reaction was stirred overnightat room temperature. The reaction mixture was then transferred to abeaker and mixed with 200 mL of water. The mixture was acidified with 1M hydrochloric acid. Then, the mixture was transferred to a separationfunnel and extracted with ethyl acetate three times (80 mL each). Theorganic phase was concentrated to collect the product.

The product obtained in the prior step was mixed with 200 mL of waterand then heated to 80° C. A 50% solution of sodium hydroxide was addedduring the course of heating to keep the pH above 12. After 4 hours, thereaction was acidified to a pH of about 2 and the product precipitatedout. The product was separated by filtration.

Preparation Example EX29

This example demonstrates the production of the lithium salt ofN-cyclobutyl-terephthalamic acid having the following structure

In a beaker, 300 mg of N-cyclobutyl-terephthalamic acid was dispersed inabout 40 mL of water. Lithium hydroxide was slowly added until the pHwas about 12. Then, the solution was concentrated to obtain the desiredproduct.

Preparation Example EX30

This example demonstrates the production of N-cyclopropyl-terephthalamicacid having the following structure

In a flask, 9.3 g of sodium carbonate, 5 g of cyclopropylamine, and 80mL of tetrahydrofuran were added. Then, 16.43 g of4-chlorocarbonyl-benzoic acid methyl ester was diluted in 30 mL of THFand then added dropwise to the reaction. The reaction was stirredovernight. The product was from the mixture with 400 mL of water. Theproduct was collected and dried, about 18 grams were obtained.

In a flask, 18 g of the product obtained in the previous step was mixedwith 200 mL of water and then heated to 80° C. A 50% solution of sodiumhydroxide was added during the course of heating to keep the pH above12. After 4 hours, the reaction was acidified to a pH of about 2 and theproduct precipitated out. The solution was filtered to obtain theproduct.

Preparation Example EX31

This example demonstrates the production of the lithium salt ofN-cyclopropyl-terephthalamic acid having the following structure

In a beaker, 2.46 g of wet N-cyclopropyl-terephthalamic acid was mixedwith 100 mL water and then lithium hydroxide monohydrate was added untilthe pH was 12. The reaction was stirred for 20 minutes and wasconcentrated to yield the product.

Preparation Example EX32

This example demonstrates the production of the calcium salt ofN-cyclopropyl-terephthalamic acid having the following structure

In a beaker, 2.51 g of N-Cyclopropyl-terephthalamic acid was mixed with50 mL water. Then, a 50% solution of sodium hydroxide was added untilthe pH was 12. The reaction was stirred for 20 minutes. Then 3.52 g ofcalcium chloride dihydrate was added to the solution to form theproduct. The product was collected by filtration and dried in an oven.

Preparation Example EX33

This example demonstrates the production of the zinc salt ofN-cyclobutyl-terephthalamic acid having the following structure

In a beaker, 2.51 g of N-cyclopropyl-terephthalamic acid was mixed with50 mL of water. Then, a 50% solution of sodium hydroxide was added untilthe pH was 12. The reaction was stirred for 20 minutes. Then, 3.27 g ofzinc chloride was added to the solution to form the product. The productwas collected by filtration and dried in an oven.

Preparation Example EX34

This example demonstrates the production of4-(4-methoxy-benzoylamino)benzoic acid having the following structure

In a 1 L three-neck flask equipped with an overhead stirrer, temperatureprobe, dry ice bath and a reflux condenser, 25 g of 4-aminobenzoic acid,45.39 g of soda ash, and 200 mL of tetrahydrofuran were added. Withstirring, 31.10 g of 4-methoxyebzoyl chloride was added dropwise over a1-1.5 hour period. The temperature was kept below 10° C. duringaddition. After completion of the reaction, the mixture was diluted with2 L of water. The pH was lowered to about 2 with hydrochloric acid toprecipitate the product. The product was collected by filtration anddried in an oven.

Preparation Example EX35

This example demonstrates the production of the sodium salt of4-(4-methoxy-benzoylamino)benzoic acid having the following structure

In a beaker, 24 g of 4-(4-methoxy-benzoylamino)benzoic acid was mixedwith 200 mL of water. Then, a 50% solution of sodium hydroxide wasslowly added until a stable pH value of 12 was obtained. The solutionwas concentrated in vacuo to provide the sodium salt of4-(4-methoxy-benzoylamino)benzoic acid.

Preparation Example EX36

This example demonstrates the production of the lithium salt of4-(4-methoxy-benzoylamino)benzoic acid having the following structure

In a beaker, 6 g of 4-(4-methoxy-benzoylamino)benzoic acid was mixedwith 100 mL of water and lithium hydroxide monohydrate was slowly addeduntil the pH stabilized at 12. The reaction was stirred for 20 minutesand then was concentrated in vacuo to provide the product.

Preparation Example EX37

This example demonstrates the production of N-cycloheptyl-terephthalamicacid having the following structure

A 1 L round bottom flask was charged with 9.3 g of sodium bicarbonate, 5g of cycloheptylamine, and 80 mL of tetrahydrofuran (THF). The flask waschilled with an ice bath. Then, a solution of 4-chlorocarbonyl-benzoicacid methyl ester (8.32 g in about 30 mL of THF) was added dropwise tothe flask. After the addition, the reaction was heated to reflux. Thereaction was monitored with IR until the peak at 1780 cm⁻¹ disappeared.Then the mixture was poured into about 400 mL of water and stirred forabout 20 minutes. The product was collected by filtration and dried inan oven at 100° C.

In a flask, 9.1 g of the product from the previous step was mixed with200 mL of water. A 50% NaOH solution was added until the pH was about12. The reaction was heated to 80° C., stirred for 4 hours, and the pHwas maintained at 12 during the reaction. After thin layerchromatography showed the completion of the reaction, the pH wasadjusted to 2 to precipitate the product. The product was filtered andwashed.

Preparation Example EX38

This example demonstrates the production of the sodium salt ofN-cycloheptyl-terephthalamic acid having the following structure

In a flask 8.8 g of N-Cycloheptyl-terephthalamic acid was mixed with 200mL of water and a 50% solution of sodium hydroxide was added slowlyuntil the pH stabilized at 12. For 20 more minutes, the solution wasstirred and then was concentrated in vacuo to yield the product.

Preparation Example EX39

This example demonstrates the production of4-(1,3-Dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-2-hydroxy-benzoic acidhaving the following structure

In a 500 mL four-neck round bottom equipped with a temperature probe,heating mantle, agitator, and condenser, 17.95 g of naphthalic anhydrideand 87 mL of acetic acid were charged. The mixture was heated to 70° C.and stirred until a clear solution was obtained. The solution was alight amber color. Then, 14.58 g of 4-aminosalicylic acid was added tothe solution. After heating at reflux for 6 hours, the reaction mixturewas poured into water. The product was collected by filtration and thenwashed with water. After drying, 22.18 g of product was obtained as atan powder.

Preparation Example EX40

This example demonstrates the production of the sodium salt of4-(1,3-dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-2-hydroxy-benzoic acidhaving the following structure

In a beaker,4-(1,3-Dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-2-hydroxy-benzoic acid wasmixed with 200 mL of water. Then a 50% solution of sodium hydroxide wasslowly added until a stable pH value of 12 was obtained. The solutionwas concentrated in vacuo to yield the sodium salt of4-(1,3-dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-2-hydroxy-benzoic acid.

Preparation Example EX41

This example demonstrates the production of the potassium salt of4-(1,3-Dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-2-hydroxy-benzoic acidhave the following structure

In a beaker,4-(1,3-Dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-2-hydroxy-benzoic acid wasmixed with 200 mL of water. Then, potassium hydroxide was slowly addeduntil a stable pH value of 12 was obtained. The solution wasconcentrated in vacuo providing the potassium salt of4-(1,3-dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-2-hydroxy-benzoic acid.

Preparation Example EX42

This example demonstrates the production ofN-(3,4-dimethyl-phenyl)-terephthalamic acid having the followingstructure

The product was prepared in a similar manner to that used in PREPARATIONEXAMPLE EX37 using the 3,4-dimethyl aniline in the place ofcycloheptylamine.

Preparation Example EX43

This example demonstrates the production of the potassium salt ofN-(3,4-Dimethyl-phenyl)-terephthalamic acid having the followingstructure

In a beaker, N-(3,4-Dimethyl-phenyl)-terephthalamic acid was mixed with200 mL of water. Then, potassium hydroxide was slowly added until astable pH of 12 and a clear solution was obtained. The solution wasconcentrated in vacuo providing the desired product.

Preparation Example EX44

This example demonstrates the production of the lithium salt ofN-(3,4-Dimethyl-phenyl)-terephthalamic acid having the followingstructure

In a beaker, N-(3,4-Dimethyl-phenyl)-terephthalamic acid was mixed with200 mL of water. Then, lithium hydroxide monohydrate was slowly addeduntil a stable pH value of 12 was obtained. The solution wasconcentrated in vacuo providing the desired product.

Preparation Example EX45

This example demonstrates the production of 4-benzoylamino benzoic acidhaving the following structure

In a 1 L beaker with mechanical stirring, 27.4 g of 4-aminobenzoic acid(0.2 mol) was mixed in 300 mL of DI H₂O. Then, 21.2 g (0.2 mol) ofsodium carbonate was added until the pH value became 9.1 and all the4-amino benzoic acid dissolved in the water.

Then, 56.24 g (0.4 mol) of benzoyl chloride was added dropwise to thebeaker at room temp. The reaction was stirred overnight. A solid formedduring the reaction, and the pH stabilized at 4.0. The pH was furtherlowered to about 2 with hydrochloric acid. The product was collected byfiltration and washed with hot water to remove excess benzoic acid. Thesolid product was dried in an oven at 110° C. and 44.21 g of the productwas obtained (yield 96.7%).

Preparation Example EX46

This example demonstrates the production of the lithium salt of4-benzoylamino benzoic acid having the following structure

In a 500 mL beaker, 44.21 g of 4-benzoamido-benzoic acid was mixed withabout 250 mL of water. Then, 7.69 g of lithium hydroxide monohydrate(dissolved in about 100 mL of water) was added. The reaction was stirredovernight and the pH value became neutral. The solid product wascollected by filtration and dried in an oven at 110° C., 39.7 g ofmaterial was obtained (yield 88%).

Preparation Example 47

This example demonstrates the production of the magnesium salt of4-benzoylamino benzoic acid having the following structure

In a 500 mL beaker, 30 g of 4-benzoamido-benzoic acid was mixed withabout 250 mL of water. Then, 6.98 g of potassium hydroxide (dissolved inabout 50 mL of water) was added. The resulting mixture was stirredovernight. All of the solids dissolved, and the pH value became neutral.Then, 25.3 g of magnesium chloride hexahydrate in about 100 mL water wasadded. The product precipitated out immediately. The mixture was stirredone more hour after the addition and then filtered to collect theproduct. The product was washed with DI water and dried in an oven at110° C.

Preparation Example EX48

This example demonstrates the production of 4-N-cyclohexyl-amidobenzoicacid having the following structure

In a 2 L round bottom flask equipped with an ice bath, 3.83 g of sodiumbicarbonate, 4.53 g of cyclohexylamine, 0.5 g of triethylamine, and 200mL of tetrahydrofuran were added. Then, 9.06 g of 4-carbomethoxybenzoylchloride (dissolved in 9.70 g of tetrahydrofuran) was added dropwiseover an hour to the flask. After addition, the reaction was gentlyheated to reflux. IR was monitored for completion of the reaction (thedisappearance of the peak at 1780 cm⁻¹). After completion, the reactionwas diluted with 2 L of H₂O, stirred 20-30 min, and then filtered tocollect the solid as the product. The product was dried in an oven at110° C.; 11.31 g of product was obtained.

To a 2 L three-necked round bottom flask, 11.31 g of the product made inthe previous step and 150 mL of methanol were added. Then, 2.72 g ofpotassium hydroxide (dissolved in methanol) was added dropwise to theflask. After completion of the addition, the reaction was heated toreflux. IR was monitored for completion of the reaction (thedisappearance of the peak at 1720 cm⁻¹). After the reaction, 750 mL ofwater was added and filtered to remove any insoluble impurities. The pHof the filtrate was adjusted to about 2 with hydrochloric acid toprecipitate the product. The mixture was filtered to collect theproduct, and the product was washed with DI water. The product was driedin an oven at 110° C.

Preparation Example EX49

This example demonstrates the production of the potassium salt of4-N-cyclohexyl-amidobenzoic acid having the following structure

In a beaker, 6 g of 4-N-cyclohexyl-amidobenzoic acid was dispersed in 50mL of H₂O. Then, 1.36 g of potassium hydroxide was dissolved in anotherbeaker with about 20 mL of H₂O and then added to the slurry. Most ofmaterial dissolved and the residual insoluble solid was removed byfiltration. The H₂O was stripped off from the filtrate to collect theproduct. The product was dried in an oven overnight at 110° C.

Preparation Example EX50

This example demonstrates the production of the aluminum salt of4-N-cyclohexyl-amidobenzoic acid having the following structure

1 gram of the potassium salt of 4-N-cyclohexyl-amidobenzoic acid wasdissolved in a beaker with about 25 mL of H₂O. In another beaker, 0.78 gof aluminum sulfate octadecahydrate was dissolved with about 15 mL ofH₂O. The two solutions were mixed and a precipitate formed instantly.The solid was collected by suction filtration and dried in an ovenovernight at 110° C.

Preparation Example EX51

This example demonstrates the production of4-(1,3-dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-benzoic acid having thefollowing structure

In a 1 L four-neck round bottom flask equipped with a temperature probe,heating mantle, agitator, and condenser, 25 g of naphthalic anhydrideand 80 mL of acetic acid were charged. After the formation of a darkred-orange solution, 17.31 g of 4-aminobenzoic acid was added and thereaction was heated to reflux overnight. The reaction mixture was pouredinto excess amount of DI water to precipitate the product. The productwas collected by filtration, washed with more DI water, and then driedin an oven.

Preparation Example EX52

This example demonstrates the production of the lithium salt of4-(1,3-dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-benzoic acid having thefollowing structure

In a 1000 mL beaker equipped with an overhead agitator, 5.09 g of4-(1,3-dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-benzoic acid and 100 mL ofDI H₂O was charged. The reaction was stirred, and the pH was adjustedwith lithium hydroxide until all the acid was in solution. Water wasremoved by rotary evaporation. 5.231 g of the product was obtained.

Preparation Example EX53

This example demonstrates the production of the lithium salt ofN-benzyl-terephthalamic acid having the following structure

In a three-neck round bottom flask fitted with a condenser and additionfunnel, 6.345 g of sodium bicarbonate, 8.09 g of benzylamine, 0.5 g oftriethylamine and 350 mL of tetrahydrofuran were added. The mixturetemperature was cooled to below 10° C. Then, 15 g of carbomethoxybenzoylchloride (dissolved in about 150 mL of tetrahydrofuran) was addeddropwise over one hour. After addition, the mixture was gently heated toreflux. The reaction was monitored to completion with IR (disappearanceof peak at 1780 cm⁻¹). Upon completion, the mixture was diluted withabout 2 L of DI water and stirred for 20-30 min. The product wascollected by filtration and dried in an oven at 100° C. 18.68 gram ofmaterial was obtained (yield 91.84%)

In a 2 L beaker, 2.12 g of the product from the previous step and 300 mLof DI water were added. Then, 1.89 g of a 10% solution of lithiumhydroxide was added and stirred until the reaction was completed(disappearance of peak at 1720 cm⁻¹ in IR). Then, all the water wasremoved by rotary evaporation to collect the product; 1.94 g of theproduct was obtained (yield 94.37%).

Preparation Example EX54

This example demonstrates the production of the lithium salt ofN-pyridin-2-yl-terephthalamic acid having the following structure

In a 250 mL three-neck round bottom flask equipped with overheadstirring, temperature probe, ice bath and reflux condenser, 4.71 g of3-aminopyridine, 4.2 g of sodium bicarbonate, about 0.1 g oftriethylamine, and 50 mL of tetrahydrofuran were added. The temperaturewas cooled to below 10° C. and then 9.9 gram of carbomethoxybenzoylchloride (a solution in 20 mL of tetrahydrofuran) was added dropwiseover 1-1.5 hours. The reaction was stirred overnight and then heated toreflux for about 2 hours. Then, 500 mL of DI water was used to dilutethe reaction and the resulting mixture was stirred for 20-30 minutes.The solid product was collected by filtration and dried in an oven at110° C.

In a 250 mL beaker equipped with a magnetic stir bar, 2.56 g of theproduct made in the previous step, 0.42 g of lithium hydroxidemonohydrate, and 50 mL of DI water were added. The beaker was heated to90° C. until the pH was below 10. The solid product was collected byfiltration and any water was removed by evaporation.

Preparation Example EX55

This example demonstrates the production ofN-(2-chloro-phenyl)-terephthalamic acid having the following structure

In a 2 L round bottom flask, 6.34 g of sodium bicarbonate, 9.63 g of2-chloroaniline, 0.5 g of triethylamine, and 200 mL of tetrahydrofuranwere added. After the reaction was cooled with an ice bath, 15 g ofcarbomethoxybenzoyl chloride (dissolved in about 100 mL of THF) wasadded dropwise to the flask. After addition, the reaction was heated toreflux. IR was monitored for completion (the disappearance of the peakat 1780 cm⁻¹). After completion, the solution was diluted with 2 L of DIH₂O and stirred 20-30 min. The solid product was collected by filtrationand dried in an oven at 110° C.

To a 2 L three-necked round bottom flask, 20.12 g of the product fromthe previous step and 150 mL of methanol were added. The reaction washeated to reflux. Upon starting heating, 3.90 g of potassium (dissolvedin methanol) was added dropwise to the reaction. IR was monitored forcompletion (the disappearance of the peak at 1720 cm⁻¹). Aftercompletion, the solution was diluted with excess H₂O. Filtration wasused to remove any residual solid, and then HCl was added to thefiltrate until the pH value was about 2. The product precipitated out atthis step, was collected by filtration, and then dried in an oven at110° C.

Preparation Example EX56

This example demonstrates the production of the lithium salt ofN-(2-chloro-phenyl)-terephthalamic acid having the following structure

In a beaker, 1 gram of N-(2-Chloro-phenyl)-terephthalamic acid wassuspended in about 20 mL water and then 0.1527 g of lithium hydroxidemonohydrate was added. The reaction was stirred until the pH decreasedto below 10. The solid product was collected by filtration.

Preparation Example EX57

This example demonstrates the production of the potassium salt ofN-(2-chloro-phenyl)-terephthalamic acid having the following structure

In a beaker, 12 gram of N-(2-Chloro-phenyl)-terephthalamic acid wassuspended in about 200 mL of water and then 2.448 g of potassiumhydroxide was added. The reaction was stirred until the pH decreased tobelow 10. The product was collected after rotary evaporation to removeexcess water.

Preparation Example EX58

This example demonstrates the production ofN-(3,5-dicyano-4-methyl-thiophen-2-yl)-terephthalamic acid having thefollowing structure

In a three-neck round bottom flask equipped with overhead stirring,temperature probe, dry ice bath and reflux condenser, 12.32 g of5-amino-3-methylthiophene-2,4-dicarbonitrile, 6.27 g of soda ash, and200 mL of tetrahydrofuran were added. The temperature was lowered tobelow 10° C. and then 30 gram of a carbomethoxybenzoyl chloride solution(50% solution in tetrahydrofuran) were added dropwise over 1-1.5 hours.After addition, the mixture was heated to about 40° C. until thereaction was complete (monitored by IR, the peak at 1780 cm⁻¹disappeared). Then, the reaction was diluted with about 2 L of DI waterand filtered to collect the product.

In a 32 oz jar equipped with a magnetic stir bar, 17.4 g of the productmade in the previous step was dissolved in 300 mL methanol. And then30.05 g of a potassium hydroxide solution (10% in methanol) was added.The reaction was monitored by IR. After the completion of the reaction,the mixture was diluted with 1 liter of water. The mixture was filteredto remove any insoluble impurities, and the filtrate was acidified withhydrochloric acid until the pH was about 2. The product precipitated outat this step. The mixture was filtered to collect the product. Theproduct washed with DI water and dried.

Preparation Example EX59

This example demonstrates the production of the sodium salt ofN-(3,5-dicyano-4-methyl-thiophen-2-yl)-terephthalamic acid having thefollowing structure

In a beaker, N-(3,5-Dicyano-4-methyl-thiophen-2-yl)-terephthalamic acidwas mixed with 200 mL of water. Then, a 25% solution of sodium hydroxidewas slowly added until a stable pH value of 12 was obtained. Thesolution was concentrated in vacuo providing the desired product.

Preparation Example EX60

This example demonstrates the production of the lithium salt ofN-(3,5-dicyano-4-methyl-thiophen-2-yl)-terephthalamic acid having thefollowing structure

In a beaker, N-(3,5-Dicyano-4-methyl-thiophen-2-yl)-terephthalamic acidwas mixed with 200 mL of water. Then, lithium hydroxide monohydrate wasslowly added until a stable pH value of 12 was obtained. The solutionwas concentrated in vacuo providing the desired product.

Preparation Example EX61

This example demonstrates the production of the zinc salt ofN-(3,5-dicyano-4-methyl-thiophen-2-yl)-terephthalamic acid having thefollowing structure

In a beaker, N-(3,5-Dicyano-4-methyl-thiophen-2-yl)-terephthalamic acidwas mixed with 200 mL of water. Then, a 25% solution of potassiumhydroxide was slowly added until a stable pH value of 12 was obtained.One equivalent of zinc chloride (dissolved in water) was then added tothe solution and the product precipitated out. The product was collectedby filtration and washed with DI water.

Preparation Example EX62

This example demonstrates the production of the lithium salt ofN-Pyridin-3-yl-terephthalamic acid having the following structure

In a 250 mL three-neck flask equipped with overhead stirring,temperature probe, ice bath and reflux condenser, 4.71 g of3-aminopyridine, 4.2 g of sodium bicarbonate, about 0.1 g oftriethylamine, and 50 mL of tetrahydrofuran were added. The temperaturewas lowered to below 10° C., and then 9.9 gram of carbomethoxybenzoylchloride (a solution in 20 mL tetrahydrofuran) was added dropwise over1-1.5 hours. The reaction was stirred overnight and then was heated toreflux for about 2 hours. Then, the reaction was diluted with about 500mL of DI water and stirred for 20-30 minutes. The solid product wascollected by filtration and dried in an oven at 110° C.

In a 250 mL beaker equipped with a magnetic stir bar, 2.56 g of theproduct made in the previous step, 0.42 g of lithium hydroxidemonohydrate, and 75 mL of DI water were added. The beaker was heated to90° C. until the pH was below 10. Any solids were removed throughfiltration, and the filtrate was collected. The product was collectedafter excess water was removed through evaporation.

Preparation Example EX63

This example demonstrates the production ofN-(2-Methoxy-phenyl)-terephthalamic acid having the following structure

In a three-neck flask equipped with overhead stirring, temperatureprobe, dry ice bath and reflux condenser, 7.44 g of o-anisidine, 5.01 gof soda ash, and 200 mL of tetrahydrofuran were added. The temperaturewas lowered to below 10° C. and then 25 gram of a carbomethoxybenzoylchloride solution (48% in tetrahydrofuran) was added dropwise over 1-1.5hours. After addition, the reaction was heated to about 40° C. until thereaction was completed (monitored by IR, the peak at 1780 cm⁻¹disappeared). Then, the mixture was diluted with about 2 L of DI water,and the product was collected by filtration.

In a 32 oz jar equipped with a magnetic stir bar, 13.95 g of the productmade in previous step was dissolved in 300 mL methanol. Then, 27.5 g ofpotassium hydroxide solution (10% in methanol) was added. The reactionwas monitored by IR. After the completion of the reaction, the mixturewas diluted with about 1 L water. Insoluble impurities were removed byfiltration. The filtrate was acidified with hydrochloric acid until thepH was about 2. The product precipitated out at this step. The productwas collected by filtration, washed with DI water, and dried.

Preparation Example EX64

This example demonstrates the production of the potassium salt ofN-(2-methoxy-phenyl)-terephthalamic acid having the following structure

In a beaker, N-(2-methoxy-phenyl)-terephthalamic acid was mixed with 200mL of water. Then, a 25% solution of potassium hydroxide was slowlyadded until a stable pH value of 12 was obtained. The solution wasconcentrated in vacuo to yield the desired product.

Preparation Example EX65

This example demonstrates the production of the magnesium salt of4-N-phenyl-terephthalamic acid having the following structure

In a 250 mL beaker equipped with a magnetic stir bar and stir plate, 10g of 4-N-phenylamidobenzoic acid and 50 mL of water were added. Thereaction was heated to near boiling and 1.5 g magnesium oxide was added.IR was used to monitor the reaction to completion, and the product wascollected by filtration.

Preparation Example EX66

This example demonstrates the production of the lithium salt of4-N-(3,4-dichlorophenyl)amidobenzoic acid having the following structure

In a 1 L three-neck round bottom flask equipped with magnetic stirring,addition funnel, ice bath, nitrogen inlet and a hotplate, 12.48 g of3,4-dichloroaniline, 6.34 g of sodium bicarbonate, 0.5 g oftriethylamine, and 200 mL of tetrahydrofuran were added. The temperaturewas lowered to below 10° C. and then 15 gram of carbomethoxybenzoylchloride (a solution in 100 mL tetrahydrofuran) was added dropwise over1-1.5 hours. After addition, the reaction was heated to about 40° C.until the reaction was complete (monitored by IR, the peak at 1780 cm⁻¹disappeared). Then, the reaction was diluted with about 2 L of DI waterand the product was collected by filtration. 23.87 g of product wasobtained (yield: 97.5%).

In a 250 mL beaker, 3 g of the product from the previous step was mixedwith 50 mL water. The mixture was heated to near boiling, and 2.22 gramof a 10% solution of lithium hydroxide was added. The reaction wasmonitored to completion by IR. The reaction mixture was evaporated tonear dryness and the product was collected by filtration. 1.92 g of theproduct was obtained (yield 65.6%).

Preparation Example EX67

This example demonstrates the production of the calcium salt of4-N-(2,6-diisopropylphenyl)amidobenzoic acid having the followingstructure

In a 1 L three-neck round bottom flask equipped with a magnetic stirrer,addition funnel, ice bath, nitrogen sweep, scrubber, and hot plate,14.73 g of 2,6-diisopropylaniline, 6.34 g of sodium bicarbonate, 0.5 gof triethylamine, and 200 mL of tetrahydrofuran were charged. Themixture was cooled to below 10° C., and then 15 g of carbomethoxybenzoylchloride (dissolved in 100 mL of tetrahydrofuran) was added dropwiseover 1-1.5 hours. After addition, the reaction was slowly heated toreflux. After the reaction was complete (disappearance of peak at 1780cm⁻¹ in IR), it was diluted with cold DI water and stirred for 20-30minutes. The product was collected by filtration and dried in an oven at110° C.

In a 600 mL beaker, 13.79 gram of the product from the previous step wasmixed in 200 mL water. The mixture was heated to near boiling, and 22.8gram of a 10% solution of potassium hydroxide was added. After thecompletion of the reaction was monitored by IR, 6.72 g of calciumchloride dihydrate (dissolved to form 10% solution) was added. Theproduct precipitated out and was collected by filtration.

Preparation Example EX68

This example demonstrates the production of4-benzoylamino-2-hydroxy-benzoic acid having the following structure

In a three-neck flask equipped with overhead stirring, temperatureprobe, dry ice bath, and a reflux condenser, 25 g of 4-aminosalicyclicacid, 5.01 g of soda ash, and 200 mL of tetrahydrofuran were added andstirred. The temperature was lowered to below 10° C., and 7.32 g benzoylchloride was added dropwise over 1-1.5 hour. After addition, the flaskwas gently heated to 40° C. After the completion of the reaction(monitored by IR as the peak at 1780 cm⁻¹ disappears), the reactionmixture was diluted with 300 mL of water. The organic layer wasseparated. After drying off the solvent, about 16 grams of product wasobtained.

Preparation Example EX69

This example demonstrates the production of the lithium salt of4-benzoylamino-2-hydroxy-benzoic acid having the following structure

In a beaker, 3 grams of 4-Benzoylamino-2-hydroxy-benzoic acid was mixedwith 20 mL of water. Then, 1.05 g of lithium hydroxide monohydrate wasadded. The mixture was stirred for 20 minutes, and then the reactionmixture was concentrated in vacuo to provide the desired lithium salt.

Preparation Example EX70

This example demonstrates the production of the calcium salt of4-benzoylamino-2-hydroxy-benzoic acid having the following structure

In a beaker, 3 grams of 4-Benzoylamino-2-hydroxy-benzoic acid was mixedwith 20 mL of water. Then, 2.51 g of a 50% sodium hydroxide solution wasadded. After the solution became clear, a solution containing 3.53 g ofcalcium chloride dehydrate was added. The product precipitated out andwas collected by filtration.

Preparation Example EX71

This example demonstrates the production of4-[(biphenyl-4-carbonyl)-amino]-benzoic acid having the followingstructure

In a 5 L three-neck round bottom flask, 316.5 g of 4-aminobenzoic acidwas dissolved in about 3 L of dioxane. Then, 250 grams ofbiphenyl-4-carbonyl chloride (dissolved in about 150 mL of dioxane) wasadded dropwise over 1 hour. The reaction was stirred overnight andfiltered to collect the solid. The solid was washed with boiling DIwater and then cold DI water until the pH of the water was aboutneutral. The washed solid was then dried in a vacuum oven.

Preparation Example EX72

This example demonstrates the production of the lithium salt of4-[(biphenyl-4-carbonyl)-amino]-benzoic acid having the followingstructure

In a beaker, 364.62 g of 4-[(biphenyl-4-carbonyl)-amino]-benzoic acidwas suspended in about 3 L of water. Then, a solution of lithiumhydroxide monohydrate (41.96 g in about 500 mL water) was added to thesuspension. The reaction was stirred overnight, and the pH value became7.5. The solid product was collected by filtration, washed with water,and dried in an oven at 110° C. 334.7 g of the product was obtained (90%yield).

Preparation Example EX73

This example demonstrates the production of4-(benzylidene-amino)-benzoic acid having the following structure

In a 500 mL three-neck round bottom flask equipped with a condenser,hearing mantle, magnetic stir and two stoppers, 10 gram of4-aminobenzoic acid, 7.75 g of benzaldehyde, and 200 mL of ethanol wereadded. The reaction mixture was heated to reflux for 6 hours. Theproduct crystallized out of solution after the solution was cooled toroom temperature. The product was collected by filtration. Additionalproduct was recovered by concentrating the filtrate. 15.41 g of theproduct was obtained (yield: 94%).

Preparation Example EX74

This example demonstrates the production of the lithium salt of4-(benzylidene-amino)-benzoic acid having the following structure

In a 2 L beaker, 15.41 of 4-(benzylidene-amino)-benzoic acid wasdissolved in 200 mL of water. The mixture was gently heated and stirredon a hot plate until a clear solution was obtained. Then, 2.85 g oflithium hydroxide monohydrate was slowly added. The solution becameslight hazy. After the completion of the reaction, it was cooled downand the water was evaporated off. A yellow solid was collected. Theproduct was washed with acetone and then dried in an oven at 110° C.

Preparation Example EX75

This example demonstrates the production of 4-chlorophenylamido-benzoicacid having the following structure

In a 5 L flask, 274.3 g of 4-aminobenzoic acid (2 mol) and 2800 mL ofacetone were added. The reaction was stirred until a uniform slurryformed. Then, 175 g of 4-chlorobenzoyl chloride was added dropwise tothe 5 L flask while the contents were being stirred. The reaction wasstirred overnight and then filtered to collect the solid. The productwas rinsed with about 500 mL of acetone and then three times with water(500 mL each time). After washing, the solid was moved to a 4 L beakerand suspended in about 2 L of boiling water for an hour. The solidproduct was collected by filtration and washed with more boiling wateruntil the water was colorless.

Preparation Example EX76

This example demonstrates the production of the sodium salt of4-chlorophenylamido-benzoic acid having the following structure

In a 2 L beaker equipped with a mechanical stirrer, 400 mL of water and27.5 g of 4-chlorophenylamido-benzoic acid were added. In anotherbeaker, 8.4 grams of NaOH (50% solution) was diluted in 100 mL of water.The NaOH solution was added to the 4-chlorophenylamido-benzoic acidsuspension, and the mixture was stirred overnight. The product wascollected by filtration. The product was washed with DI water until thepH of the water was below 10, and the product was then dried in an ovenat 110° C.

Preparation Example EX77

This example demonstrates the production of4-(4-fluoro-benzoylamino)-benzoic acid having the following structure

In a 4 L beaker, 21.27 g of 4-aminobenzoic acid and 1 L of DI H₂O wereadded. Then, 33.38 g of sodium carbonate was added. Next, 100 g of4-fluorobenzoyl chloride was added dropwise to flask (over about 45min-1 h) and the reaction was stirred overnight. The solid product wascollected by vacuum filtration and washed with boiling water to removeexcess 4-fluorobenzoic acid. The product was dried overnight in a vacuumoven. 59.08 g of product was obtained.

Preparation Example EX78

This example demonstrates the production of the lithium salt of4-(4-fluoro-benzoylamino)-benzoic acid having the following structure

In a beaker, 10 gram of 4-(4-fluoro-benzoylamino)benzoic acid wassuspended in 100 mL of DI water. Then, 1.62 g of lithium hydroxidemonohydrate was first dissolved in 25 mL of DI water and then added intothe acid suspension. The reaction was stirred overnight and the productwas collected by evaporating off the water.

Preparation Example EX79

This example demonstrates the production of4-benzoylamino-2,3,4,5-tetrafluoro-benzoic acid having the followingstructure

In a 250 mL flask equipped with a stirrer, 3.37 g of4-amino-2,3,4,5-tetrafluoro benzoic acid, 1.06 g of sodium carbonate,and 20 mL of water were added. Then, 6.8 g of 4-benzoyl chloride wasadded dropwise to the flask (over about 45 min-1 h). The pH was recordedbelow 1 the next morning. The solid product was collected by filtration,washed with DI water 5 times, and then dried in an oven at 110° C.

Preparation Example EX80

This example demonstrates the production of the lithium salt of4-(4-fluoro-benzoylamino)-benzoic acid having the following structure

In a 250 mL beaker, 2 gram of 4-Benzoylamino-2,3,4,5-tetrafluoro-benzoicacid and 20 mL of DI water were added. Then, 0.27 g of lithium hydroxidemonohydrate was first dissolved in 10 mL of DI water and then added intothe acid suspension. The reaction was stirred overnight, and the productwas collected by evaporating off the water.

Preparation Example EX81

This example demonstrates the production of benzene-1,3,5-tricarboxylicacid tris-(4-carboxybenzene)amide having the following structure

In a three neck round bottom flask, 21.2 g of sodium carbonate and 100mL of tetrahydrofuran were added. Then, 13.75 g of 4-aminobenzoic acidand 8 g of 1,3,5-benzenetricarbonyl trichloride were each separatelydiluted in 15 mL of THF and added into the reaction simultaneously viatwo addition funnels. The reaction was stirred overnight at roomtemperature. About 80 mL of tetrahydrofuran was added to compensate theevaporation during the reactions and an additional 10.6 gram of sodiumcarbonate was added. Three hours later, the reaction was transferred toa 1 L beaker with 600 mL of water. The pH was adjusted to about 2 withhydrochloric acid. The product precipitated out and was collected byfiltration. The product was then partially dried in a vacuum oven at 40°C. About 35 gram of wet product was obtained.

Preparation Example EX82

This example demonstrates the production of the sodium salt ofbenzene-1,3,5-tricarboxylic acid tris-(4-carboxybenzene)amide having thefollowing structure

In a beaker, 32 grams of benzene-1,3,5-tricarboxylic acidtris-(4-carboxybenzene)amide was mixed with 200 mL of water. Then, a 50%sodium hydroxide solution was slowly added to the mixture until the pHwas 12. The mixture was stirred for 20 minutes and then was concentratedin vacuo to yield the product.

Preparation Example EX83

This example demonstrates the production of biphenyl-4,4′-dicarboxylicacid bis-(4-carboxybenezene)amide having the following structure

In a three neck round bottom flask, 5.67 g of sodium carbonate and about40 mL of tetrahydrofuran were added. Then, 4.9 g of 4-aminobenzoic acidand 5.0 g of 4,4′-Biphenyldicarbonyl chloride were each separatelydiluted in 15 mL of THF and then added to the reaction simultaneouslyvia two addition funnels. The reaction was stirred overnight at roomtemperature. Then, the reaction was transferred to a 1 L beaker with 600mL of water. The pH was adjusted to about 2 with hydrochloric acid. Theproduct precipitated out and was collected by filtration. The productwas dried in vacuum oven at 50° C.

Preparation Example EX84

This example demonstrates the production of the sodium salt ofbiphenyl-4,4′-dicarboxylic acid bis-(4-carboxybenezene)amide having thefollowing structure

In a beaker, 12 grams of acid (biphenyl-4,4′-dicarboxylic acidbis-(4-carboxybenezene)amide was mixed with 100 mL of water. Then, a 50%sodium hydroxide solution was slowly added to the mixture until the pHwas 12.5. The mixture was stirred for 20 minutes and then wasconcentrated in vacuo to yield the product.

Preparation Example EX85

This example demonstrates the production of4-(4-methyl-benzoylamino)benzoic acid having the following structure

In a 5 L three neck round bottom flask, 274 g of 4-aminobenzoic acid and3000 mL of acetone were added. The mixture was stirred to form a clearsolution. Then, 154.5 g of 4-methylbenzoyl chloride was added dropwiseto the reaction. After addition, the reaction stirred overnight and thenwas filtered to collect the solid. The solid was washed with boilingwater and then cold DI water until the pH of the water was neutral. Theproduct was dried at 110° C.

Preparation Example EX86

This example demonstrates the production of the lithium salt of4-(4-methyl-benzoylamino)benzoic acid having the following structure

In a beaker, 25.5 g of 4-(4-methyl-benzoylamino)benzoic acid and 200 mLof DI water were added. The mixture was stirred until it formed auniform slurry. Then, 4.2 g of lithium hydroxide monohydrate was added.The reaction was stirred overnight, and the pH value dropped to 10. Thesolid product was filtered and then dried in an oven at 110° C.

Preparation Example EX87

This example demonstrates the production of the lithium salt ofN-cyclopentyl-terephthalamic acid having the following structure

In a beaker, 23.3 g of N-cyclopentyl-terephthalamic acid was added to100 mL of H₂O. Then, 4.2 g of lithium hydroxide monohydrate wasdissolved in a separate beaker with about 50 mL of H₂O. The lithiumhydroxide solution was added to the N-cyclopentyl-terephthalamic acidslurry and stirred until the pH value was about neutral. The product waspartially soluble in water. The water was removed by evaporation toyield the product. The product was dried overnight in an oven at 110° C.

Preparation Example EX88

This example demonstrates the production of the lithium salt of4-(cyclopentanecarbonyl-amino)-benzoic acid having the followingstructure

In a 1 liter 2-neck roundbottom flask, 40 grams of 4-aminobenzoic acidwas dissolved in about 400 mL of dioxane. Then, 19.35 g ofcyclopentanecarbonyl chloride was added dropwise to the solution. Thereaction intermediate, 4-(cyclopentanecarbonyl-amino)-benzoic acid,formed as a white solid in the step and was collected by filtration.After washing the product with about 200 mL dioxane and then with about1 liter of boiling water, the reaction intermediate was dried in an ovenat 110° C. The yield at this step was about 27.7 g (81%).

The 27.7 gram of 4-(cyclopentanecarbonyl-amino)-benzoic acid wassuspended in about 277 mL of water. Then, 5 grams of lithium hydroxidemonohydrate was added. The mixture was stirred overnight, and the pHbecame about 7. After evaporating off the excess water, the finalproduct (the lithium salt of 4-(cyclopentanecarbonyl-amino)-benzoicacid) was collected as a white solid and dried in an oven at 110° C.

Example T1

Various additives from the Preparation Examples above were individuallypulverized and mixed with a high density polyethylene polymer having adensity of approximately 0.952 g/cm³ and a melt flow index ofapproximately 19 dg/minute (ExxonMobil™ HDPE HD 6719). Then the mixturewas either inject molded into bars or cast into thin films. The peakpolymer recrystallization temperature (T_(c)) for each thermoplasticpolymer composition was measured using a differential scanningcalorimeter (Mettler-Toledo DSC822 differential scanning calorimeter).In particular, a sample was taken from the target part and heated at arate of 20° C./minute from a temperature of 60° C. to 220° C., held at220° C. for two minutes, and cooled at a rate of approximately 10°C./minute to a temperature of 60° C. The temperature at which peakpolymer crystal reformation occurred (which corresponds to the peakpolymer recrystallization temperature) was recorded for each sample andis reported in Table 1 below.

Comparative example CTCEX1 is the high density polyethylene polymerhaving a density of approximately 0.952 g/cm³ and a melt flow index ofapproximately 19 dg/minute (ExxonMobil™ HDPE HD 6719), which wasinjection molded into sample bars. Comparative example CTCEX2 and CTCEX3are the same high density polyethylene polymer containing 1000 ppm ofsodium benzoate and aluminum bis[4-1(1,1-dimethylethy)benzoate]hydroxide(Al-pTBBA), respectively. Comparative example CTCEX4 is the same highdensity polyethylene polymer cast into a film. The examples TCEX1 toexample TCEX56 are the high density polyethylene polymer cast filmcontaining 1500 ppm of the Preparation Examples as disclosed in thisapplication.

TABLE 1 Peak polymer recrystallization temperature (T_(c)) of variousadditives in PE. T_(c) improvement Example # Additive (° C.) CTCEX1 None0.0 CTCEX2 sodium benzoate −0.7 CTCEX3 Al-pTBBA 0.0 CTCEX4 None 0.0TCEX1 EX3 2.0 TCEX2 EX5 3.0 TCEX3 EX7 1.8 TCEX4 EX8 2.5 TCEX5 EX9 2.2TCEX6 EX11 2.8 TCEX7 EX12 1.7 TCEX8 EX13 2.7 TCEX9 EX15 1.7 TCEX10 EX171.8 TCEX11 EX18 1.5 TCEX12 EX20 1.2 TCEX13 EX21 2 TCEX14 EX22 2 TCEX15EX24 1.2 TCEX16 EX26 1.7 TCEX17 EX27 1.5 TCEX18 EX29 2.7 TCEX19 EX31 2.5TCEX20 EX32 1.5 TCEX21 EX33 1.8 TCEX22 EX35 1.5 TCEX23 EX36 2.7 TCEX24EX38 2.3 TCEX25 EX40 2.0 TCEX26 EX41 1.7 TCEX27 EX43 1.8 TCEX28 EX44 1.0TCEX29 EX46 1.8 TCEX30 EX47 1.7 TCEX31 EX50 1.7 TCEX32 EX52 1.5 TCEX33EX53 1.5 TCEX34 EX54 1.0 TCEX35 EX56 1.3 TCEX36 EX57 1.5 TCEX37 EX59 1.5TCEX38 EX60 1.3 TCEX39 EX61 1.2 TCEX40 EX62 1.7 TCEX41 EX64 1.2 TCEX42EX65 0.8 TCEX43 EX66 1.0 TCEX44 EX67 0.8 TCEX45 EX69 0.8 TCEX46 EX70 0.8TCEX47 EX72 2.5 TCEX48 EX74 1.8 TCEX49 EX76 2.5 TCEX50 EX78 2.3 TCEX51EX79 1.2 TCEX52 EX82 1.7 TCEX53 EX84 2.0 TCEX54 EX86 2.2 TCEX55 EX87 3.3TCEX56 EX88 2.5

From Table 1, it is clear that all the metal salt compounds of theinvention can increase the recrystallization temperature (T_(c)) ofpolyethylene to some degree. While T_(c) is not the only importantfactor when choosing a suitable nucleator for a semi-crystallinethermoplastic polymer, the improvement in T_(c) is very desirable as itimproves crystallization rate during processing, shortens cycle time,and improves production efficiency.

Manufacture of Nucleated Blown Films

For all the blown film examples, the polyethylene resins used were firstground to about a 35 mesh powder. Then, 1000 ppm of Irganox 1010, 800ppm of Irgafos 168, 1000 ppm of DHT4-A, and the inventive nucleatingagent were added to the resin and blended in a Henschel high intensitymixer for about 2 minutes with a blade speed of about 2100 rpm. Thesamples were then melt compounded in a MPM single screw extruder with a38 mm diameter screw. The barrel temperature of the extruder was rampedfrom 160 to 190° C. The extrudate in the form of strands, was cooled ina water bath and then subsequently pelletized.

Films were produced in a pilot scale blown film line, with a 4 inmonolayer die, using a 2 mm die gap. The line included a Future Designdual lip air ring with chilled air. The extruder had a 55 mm diameterbarrier screw, with a length to width ratio of 24:1. The barreltemperature of the extruder was ramped up from 190 to 220° C.

Testing of Nucleated Polyethylene Blown Films

The % haze of the parts was measured using a BYK Gardner Haze meter,according to ASTM D1023. The clarity of the parts was measured using aBYK Gardner Haze meter. Permeation, measured as Water Vapor TransmissionRate, was measured using an Illinois Instruments 7000 Water VaporPermeation Analyzer, according to ASTM E398. Tear strength was measuredusing a ProTear tear tester according to ASTM D1922. Dart drop impacttesting was performed using a Dynisco Model D2085AB-P dart drop polymertester, according to ASTM D1709. Film tensile test was performed using aMTS Q-Test-5 instrument, according to ASTM D882.

The peak polymer recrystallization temperature (T_(c)) for thethermoplastic polymer compositions was measured using a differentialscanning calorimeter (Mettler-Toledo DSC822 differential scanningcalorimeter). In particular, a compression molded plaque was preparedfrom the pellets, and a sample was taken from the plaque and heated at arate of 20° C./minute from a temperature of 60° C. to 220° C., held at220° C. for two minutes, and cooled at a rate of approximately 10°C./minute to a temperature of 60° C. The temperature at which peakpolymer crystal reformation occurred (which corresponds to the peakpolymer recrystallization temperature) was recorded for each sample.

Example F1

This example demonstrates some of the physical properties exhibited by ahigh density polyethylene polymer that has been nucleated with anucleating agent according to the invention. Polymer compositions wereprepared by compounding (as described above) 2000 ppm of EX5 into acommercially-available, high density polyethylene polymer (Sclair® 19Gfrom Nova Chemicals) having a density of approximately 0.962 g/cm³ and amelt flow index of approximately 1.2 dg/minute. The formed polymercomposition pellet was then used to produce blown films (3 milthickness) using the following setup: 101.6 mm (4 in) die, 2.0 mm diegap, BUR 2.3, DDR 11.4, and output 30 kg/h. The peak polymerrecrystallization temperature, permeation, tear strength, dart dropimpact, 1% secant modulus, and optical properties of the resulting filmswere measured and are reported in Tables F1 to F4.

Example F2

Example F2 was prepared the same way as example F1 except EX46 was usedin the place of EX5.

Example F3

Example F3 was prepared the same way as example F1 except EX76 was usedin the place of EX5.

Comparative Example CF1

Comparative example CF1 was prepared the same way as example F1 exceptno nucleating agent was used.

TABLE F1 Peak polymer recrystallization temperature (T_(c)), vaporpermeation, and dart drop impact of comparative example CF1 and examplesF1, F2, and F3. loading T_(c) Permeation Impact Sample Additive (ppm) (°C.) (g · mil/m² · day) (g) CF1 None 115.2 3.9 95 F1 EX5 2000 120.2 5.8119 F2 EX46 2000 119.2 5.0 133 F3 EX76 2000 118.8 1.7 94

TABLE F2 Haze and clarity of comparative example CF1 and examples F1,F2, and F3. Standard loading Haze deviation Standard Sample Additive(ppm) (%) (%) Clarity deviation CF1 None 49.9 2.1 93.4 0.7 F1 EX5 200042.3 1.2 96.3 0.3 F2 EX46 2000 43.0 0.4 96.5 0.2 F3 EX76 2000 36.0 0.796.2 0.1

TABLE F3 1% secant modulus of comparative example CF1 and examples F1,F2, and F3. Machine Direction Transverse Direction 1% secant Standard 1%secant Standard Addi- Loading modulus deviation modulus deviation Sampletive (ppm) (MPa) (MPa) (MPa) (MPa) CF1 None 583 19 704 42 F1 EX5 2000639 31 607 69 F2 EX46 2000 513 29 514 8 F3 EX76 2000 684 58 616 48

TABLE F4 Tear strength of comparative example CF1 and examples F1, F2,and F3. Machine Direction Transverse Direction loading Tear StandardTear Standard Sample Additive (ppm) Strength (g) deviation (g) Strength(g) deviation (g) CF1 None 60 3 168 4 F1 EX5 2000 88 3 134 3 F2 EX462000 86 4 147 6 F3 EX76 2000 78 5 85 2

From the data in Tables F1-F4, it is clear that all the additives, EX5,EX46, and EX76 increased the peak polymer recrystallization temperature,lowered the haze, and increased the clarity. In addition, EX5 and EX46increased the machine direction tear strength, dart drop impact, andvapor permeation. EX76 also increased the machine tear resistance. Moreimportantly, EX76 generated balanced tear strength in the machine andtransverse directions, improved barrier property (evidenced by the lowerpermeation number), and improved machine direction stiffness (1% secantmodulus).

Example F4

This example demonstrates some of the physical properties exhibited by alinear low density polyethylene polymer that has been nucleated with anucleating agent according to the invention. Polymer compositions wereprepared compounding (as described above) 2000 ppm of EX5 into acommercially-available, butene linear low density polyethylene polymer(ExxonMobil™ LLDPE LL 1001.32) having a density of approximately 0.918g/cm³ and a melt flow index of approximately 1.0 dg/minute. The formedpolymer composition pellet was then used to produce blown films (2 milthickness) using the following setup: 101.6 mm (4 in) die, 2.0 mm diegap, BUR 2.35, DDR 17, and output 30 kg/h. The peak polymerrecrystallization temperature, permeation, dart drop impact, 1% secantmodulus, and tear strength were measured and are reported in Tables F5and F6.

Example F5

Example F5 was prepared the same way as example F4 except EX46 was usedin the place of EX5.

Example F6

Example F6 was prepared the same way as example F4 except EX76 was usedin the place of EX5.

Comparative Example CF2

COMPARATIVE EXAMPLE CF2 was prepared the same way as example F4 exceptno nucleating agent was used.

TABLE F5 Peak polymer recrystallization temperature (T_(c)), vaporpermeation, and dart drop impact of comparative example CF2 and samplesF4, F5, and F6. loading T_(c) Permeation Impact Sample Additive (ppm) (°C.) (g · mil/m² · day) (g) CF2 None 105.5 17.21 203 F4 EX5 2000 112.017.53 206 F5 EX46 2000 111.0 15.94 215 F6 EX76 2000 111.5 10.66 208

TABLE F6 1% Secant modulus and tear strength of comparative sample CF2and samples F4, F5, and F6. Machine Transverse Machine TransverseDirection Direction Direction Direction 1% Std Std Tear Tear Secant Dev1% Secant Dev Strength Std Dev Strength Std Dev Sample (MPa) (MPa) (MPa)(MPa) (g) (g) (g) (g) CF2 169 5 197 6 388 22 578 16 F4 174 6 174 8 43635 579 33 F5 170 7 180 6 431 21 575 23 F6 196 8 214 12 399 53 569 48

From the data in Tables F5 and F6, it is clear that the additives, EX5,EX46, and EX76 increased the peak polymer recrystallization temperature.EX5 and EX46 increased the machine direction tear strength and EX76significantly increased the machine direction modulus. All threenucleating agents of the invention increase the dart impact resistanceslightly.

Example F7

This example demonstrates some of the physical properties exhibited by alinear low density polyethylene polymer that has been nucleated with anucleating agent according to the invention. Polymer compositions wereprepared by compounding (as described above) 2000 ppm of EX46 into acommercially-available, linear low density polyethylene polymer (Dowlex™2056G) having a density of approximately 0.922 g/cm³ and a melt flowindex of approximately 1.0 dg/minute. The formed polymer compositionpellet was then used to produce blown films (1 mil thickness) using thefollowing setup: 101.6 mm (4 in) die, 2.0 mm die gap, BUR 2.38, DDR 33,and output 22 kg/h. The peak polymer recrystallization temperature,permeation, dart drop impact, 1% secant modulus, and tear strength weremeasured and are reported in Tables F7 and F8.

Comparative Example CF3

Comparative example CF3 was prepared the same way as example F7 exceptno nucleating agent was used.

TABLE F7 Peak polymer recrystallization temperature (T_(c)), vaporpermeation, and dart drop impact of comparative sample CF3 and samplesF7. loading T_(c) Permeation Impact Sample Additive (ppm) (° C.) (g ·mil/m² · day) (g) CF3 None 104.0 17.3 236 F7 EX46 2000 112.0 19.2 333

TABLE F8 1% Secant Modulus and tear strength of comparative sample CF3and samples F7. Machine Transverse Machine Transverse DirectionDirection Direction Direction 1% Std Std Tear Tear Secant Dev 1% SecantDev Strength Std Dev Strength Std Dev Sample (MPa) (MPa) (MPa) (MPa) (g)(g) (g) (g) CF3 159 5 171 5 433 32 707 21 F7 156 5 152 3 476 20 618 12

From the data in Tables F7 and F8, it is clear that the additive EX46increased the peak polymer recrystallization temperature, increased themachine direction tear strength, and dart drop impact.

Example F8

This example demonstrates some of the physical properties exhibited by alinear low density polyethylene polymer that has been nucleated with anucleating agent according to the invention. Polymer compositions wereprepared by compounding (as described above) 2000 ppm of EX76 into acommercially-available, linear low density polyethylene polymer (Dowlex™2056G) having a density of approximately 0.922 g/cm³ and a melt flowindex of approximately 1.0 dg/minute. The formed polymer compositionpellet was then used to produce blown films (3 mil thickness) using thefollowing setup: 101.6 mm (4 in) die, 2.0 mm die gap, BUR 2.38, DDR 11,and output 23 kg/h. The peak polymer recrystallization temperature,permeation, dart drop impact, dart drop impact, 1% secant modulus, andtear strength were measured and are reported in Tables F9 and F10.

Comparative Example CF4

Comparative example CF4 was prepared the same way as example F8 exceptno nucleating agent was used.

TABLE F9 Peak polymer recrystallization temperature (T_(c)) and dartdrop impact of comparative sample CF4 and samples F8. loading T_(c)Permeation Impact Sample Additive (ppm) (° C.) (g · mil/m² · day) (g)CF4 None 104.0 18.5 725 F8 EX76 2000 111.3 10.5 757

TABLE F10 1% Secant Modulus and tear strength of comparative sample CF4and samples F8. Machine Transverse Machine Transverse DirectionDirection Direction Direction 1% Std Std Tear Tear Secant Dev 1% SecantDev Strength Std Dev Strength Std Dev Sample (MPa) (MPa) (MPa) (MPa) (g)(g) (g) (g) CF4 174 4 183 3 1587 47 1771 76 F8 224 15 172 3 1421 51 134129

From the data in Tables F9 and F10, it is clear that additive EX76increased the crystalline peak temperature, dart drop impact, and MD 1%secant modulus. Also, it provides a balanced tear strength in themachine and transverse directions.

Example F9

This example demonstrates some of the physical properties exhibited by alinear low density polyethylene polymer that has been nucleated with anucleating agent according to the invention. Polymer compositions wereprepared by compounding (as described above) 2000 ppm of EX5 into acommercially-available, linear low density polyethylene polymer (DowElite™ 5100G) having a density of approximately 0.922 g/cm³ and a meltflow index of approximately 0.85 dg/minute. The formed polymercomposition pellet was then used to produce blown films (2 and 3 milthickness) the following setup: 101.6 mm (4 in) die, 2.0 mm die gap, BUR2.38, DDR 16.5 and 11 respectively for 2 mil and 3 mil films, and output30 kg/h. The peak polymer recrystallization temperature, permeation, 1%secant modulus, and tear strength were measured and are reported inTables F11 and F12.

Example F10

Example F10 was prepared the same way as example F9 except EX46 was usedin the place of EX5.

Example F11

Example F11 was prepared the same way as example F9 except EX76 was usedin the place of EX5.

Comparative Example CF5

Comparative example CF1 was prepared the same way as example F9 exceptno nucleating agent was used.

TABLE F11 Peak polymer recrystallization temperature (T_(c)) and vaporpermeation of comparative sample CF1 and samples F9, F10, and F11.loading T_(c) Permeation Sample Additive (ppm) (° C.) Thickness (g ·mil/m² · day) CF5 None 106.3 2 mil 15.6 3 mil 13.7 F9 EX5 2000 114.3 2mil 15.7 3 mil 15.4 F10 EX46 2000 113.5 2 mil 17.6 3 mil 15.8 F11 EX762000 112.7 2 mil 10.8 3 mil 9.8

TABLE F12 Tear strength of comparative sample CF1 and samples F9, F10,and F11. Machine Transverse Machine Transverse Direction DirectionDirection Direction Tear Std Tear Std 1% Std 1% Std Thickness Strengthdev Strength dev Secant Dev Secant Dev Sample (mil) (g) (g) (g) (g)(MPa) (MPa) (MPa) (MPa) CF5 2 721 33 1057 26 165 5 177 5 3 1089 37 151834 171 4 184 10 F9 2 720 26 1083 16 159 4 164 5 3 1214 43 1645 22 166 5180 7 F10 2 774 30 1100 24 159 3 172 8 3 1173 57 1608 31 170 6 178 7 F112 632 25 921 21 228 19 181 5 3 1030 40 1276 23 239 3 178 9

From the data in Tables F11-F12, it is clear that additives, EX5, EX46,and EX76 increased the peak polymer recrystallization temperature. Inaddition, EX5 and EX46 increased the machine direction tear strength,especially when the film was 3 mil thick. EX76 increased the tensilemodulus in the machine direction and generated more balanced tearstrength in the machine and transverse directions. EX5 and EX46increased the permeation while EX76 reduced permeation.

Manufacture of Nucleated Polyethylene by Injection Molding

In the following injection molding examples, the polyethylene resinsused were first ground to a 35 mesh powder. Then, the inventivenucleating agent was added to the resin and blended in a Henschel highintensity mixer for about 2 minutes with a blade speed of about 2100rpm. The samples were then melt compounded on a DeltaPlast single screwextruder, with a 25 mm diameter screw and a length to diameter ratio of30:1. The barrel temperature of the extruder was ramped from 160 to 190°C. and the screw speed was set at about 130 rpm. The extrudate in theform of a strand, was cooled in a water bath and then subsequentlypelletized.

Plaques and bars were formed through injection molding on an Arburg 40ton injection molder with a 25.4 mm diameter screw. The barreltemperature of the injection molder was 230° C. unless otherwisespecified and the mold temperature was controlled at 25° C.

Unless otherwise specified, the injection speed for the plaques was 2.4cc/sec, and their dimensions are about 60 mm long, 60 mm wide and 2 mmthick. These plaques were used to measure recrystallization temperature,bi-directional stiffness, and multi-axial impact resistance.

Unless otherwise specified, the injection speed for the bars was 15cc/sec, and their dimensions are about 127 mm long, 12.7 mm wide and 3.3mm thick. These bars were used to measure 1% secant modulus, HDT andIzod impact resistance.

Testing of Nucleated Polyethylene

Flexural properties testing (reported as bi-directional modulus) wasperformed on the above mentioned plaques using an MTS Q-Test-5instrument with a span of 32 mm, a fixed deflection rate of 8.53mm/minute, and a nominal sample width of 50.8 mm. Samples were preparedby cutting square sections (approximately 50 mm×50 mm) from the centersof the plaques in order to obtain an isotropically sized sample. Inaddition to testing the samples across the machine/flow direction as iscustomary (labeled as “Transverse Direction” in the results table),samples were also tested by flexing across the transverse direction toflow to measure stiffness in that direction as well (labeled as “MachineDirection” in the results table) in order to examine the bi-directionalstiffness of the plaques.

Multi-axial Impact testing was performed in the above mentioned plaquesusing an Instron Ceast 9350 tester according to ISO 6603 standard, usinga 2.2 m/sec speed and a chamber temperature of −30° C. Flexural modulustesting (reported as 1% secant modulus) was performed in the abovementioned bars using a MTS Qtest/5 instrument, according to ASTM D790procedure B. Heat deflection temperature was performed in the abovementioned bars using a Ceast HDT 3 VICAT instrument, according to ASTMD648-07 method B. Izod impact testing was performed in the abovementioned bars, using a Tinius-Olsen 892T instrument, according to ASTMD256, method A.

The peak polymer recrystallization temperature (T_(c)) for thethermoplastic polymer compositions was measured using a differentialscanning calorimeter (Mettler-Toledo DSC822 differential scanningcalorimeter). In particular, a sample was taken from the target part andheated at a rate of 20° C./minute from a temperature of 60° C. to 220°C., held at 220° C. for two minutes, and cooled at a rate ofapproximately 10° C./minute to a temperature of 60° C. The temperatureat which peak polymer crystal reformation occurred (which corresponds tothe peak polymer recrystallization temperature) was recorded for eachsample.

Example I1-I3

These examples demonstrate some of the physical properties exhibited bya high density polyethylene polymer that has been nucleated withnucleating agents according to the invention. Polymer compositions wereprepared by compounding (as described above) Preparation Example EX5 anddifferent acid scavengers into a commercially available high densitypolyethylene (Dowlex™ IP 40) having a density of approximately 0.954g/cm³ and a melt flow index of approximately 40 dg/minute. The resin wasfirst ground, mixed with the additives, and then compounded and extrudedto form pellets. The formed polymer composition pellet was theninjection molded into testing plaques and bars.

The formulation information for Examples I1 to I3 and ComparativeExample CI1 is listed in table I1. The peak polymer recrystallizationtemperature (T_(c)), multi-axial impact at temperatures of −30° C. andbi-directional modulus (measured on plaques), and 1% secant modulus andheat deflection temperature (measured on bars) are reported in Tables I2and I3 below.

TABLE I1 Formulation information for Samples CI1, I1, I2 and I3.Additives Examples EX5 Zinc Stearate DHT-4A CI1 None None None I1 1500ppm None None I2 1500 ppm 1500 ppm None I3 1500 ppm None 500 ppm

TABLE I2 Multi-axial impact at temperature of −30° C. and bi-directionalmodulus of sample CI1, I1, I2 and I3. Property Multi-Axial Impact (2.2m/s at −30° C.) Bi-directional Modulus Total Std Machine Std TransverseStd Energy Dev Ductility Std Direction Dev Direction Dev Sample (J) (J)Index Dev (MPa) (MPa) (MPa) (MPa) CI1 12.0 0.5 2.6 0.5 988 6 1060 3 I115.5 0.8 7.8 1.5 1069 2 1053 15 I2 13.4 1.5 4.3 1.7 979 12 1129 10 I316.7 1.2 13.1 3.8 1058 3 1062 6

TABLE I3 1% secant modus, heat deflection temperature, and peak polymerrecrystallization temperature of CI1, I1, I2, and I3. Property 1% SecantStd Dev Heat Deflection T_(c) Sample Modulus (MPa) (MPa) temperature (°C.) (° C.) CI1 810 1 61 116.0 I1 862 14 69 117.8 I2 788 4 61 117.7 I3856 12 68 118.3

Example I4-I6

These examples demonstrate some of the physical properties exhibited bya high density polyethylene polymer that has been nucleated withnucleating agents according to the invention. Polymer compositions wereprepared by compounding (as described above) Preparation Example EX46and different acid scavengers into commercially available high densitypolyethylene (Dowlex™ IP 40) having a density of approximately 0.954g/cm³ and a melt flow index of approximately 40 dg/minute. The resin wasfirst ground, mixed with the additives, and then compounded and extrudedto form pellets. The formed polymer composition pellet was theninjection molded into testing plaques and bars. The formulationinformation for examples I4 to I6 and Comparative Example CI2 is listedin Table I4. The peak polymer recrystallization temperature (T_(c)),multi-axial impact at temperature of −30° C. and bi-directional modulus(measured on plaques), and 1% secant modulus and heat deflectiontemperature (measured on bars) are reported in Table I5 and I6 below.

TABLE I4 Formulation information for Samples CI2, I4, I5 and I6.Additives Calcium Examples EX46 Stearate DHT-4A CI2 None None None I41500 ppm None None I5 1500 ppm 1500 ppm None I6 1500 ppm None 500 ppm

TABLE I5 Multi-axial impact at temperature of −30° C. and bi-directionalmodulus of sample CI2, I4, I5 and I6 Property Multi-Axial Impact (2.2m/s at −30° C.) Bi-directional Modulus Total Std Machine Std TransverseStd Energy Dev Ductility Std Direction Dev Direction Dev Sample (J) (J)Index Dev (MPa) (MPa) (MPa) (MPa) CI2 13.1 0.8 4.0 1.2 946 10 1017 14 I418.1 1.5 12.7 4.8 978 8 991 3 I5 16.8 1.2 8.7 3.5 946 15 1022 1 I6 17.50.4 10.2 2.5 998 13 1009 5

TABLE I6 1% secant modus, peak polymer recrystallization temperature,and heat deflection temperature of CI2, I4, I5 and I6. Property 1%Secant Std Dev Heat Deflection T_(c) Sample Modulus (MPa) (MPa)temperature (° C.) (° C.) CI2 839 7 63 116.2 I4 882 5 67 117.2 I5 850 865 117.2 I6 879 6 68 118.0

Example I7

This example demonstrates some of the physical properties exhibited by ahigh density polyethylene polymer that has been nucleated withnucleating agents according to the invention. Polymer compositions wereprepared by compounding (as described above) Preparation Example EX76into a commercially available high density polyethylene (Dowlex™ IP 40)having a density of approximately 0.954 g/cm³ and a melt flow index ofapproximately 40 dg/minute. The resin was first ground, mixed with theadditives, and then compounded and extruded to form pellets. The formedpolymer composition pellet was then injection molded into testingplaques and bars. The formulation information for Example I7 andComparative Example CI3 is listed in Table I7. The peak polymerrecrystallization temperature (T_(c)), multi-axial impact at temperatureof −30° C. and bi-directional modulus (measured on plaques), and 1%secant modulus and heat deflection temperature (measured on bars) weremeasured and reported in Table I8 and I9 below.

TABLE I7 Formulation information for Samples CI3 and I7. AdditivesCalcium Examples EX76 Stearate DHT-4A CI3 None None None I7 2000 ppmNone None

TABLE I8 Multi-axial impact at temperature of −30° C. and bi-directionalmodulus of samples CI3 and I7 Property Multi-Axial Impact (2.2 m/s at−30° C.) Bi-directional Modulus Total Std Machine Std Transverse StdEnergy Dev Ductility Std Direction Dev Direction Dev Sample (J) (J)Index Dev (MPa) (MPa) (MPa) (MPa) CI3 11.6 4.9 3.0 0.7 931 15 957 11 I717.3 0.9 14.0 5.0 918 8 989 12

TABLE I9 1% secant modulus, heat deflection temperature, and peakpolymer recrystallization temperature of CI3 and I7. Property 1% SecantStd Dev Heat Deflection T_(c) Sample Modulus (MPa) (MPa) temperature (°C.) (° C.) CI3 805 1 61 116.3 I7 888 14 70 117.7

Example I8-I10

These examples demonstrate some of the physical properties exhibited bya high density polyethylene polymer that has been nucleated withnucleating agents according to the invention. Polymer compositions wereprepared by compounding (as described above) Preparation Example EX5 anddifferent acid scavengers into a commercially available high densitypolyethylene (ExxonMobil™ HDPE HD 6719) having a density ofapproximately 0.952 g/cm³ and a melt flow index of approximately 19dg/minute. The resin was first ground, mixed with the additives, andthen compounded and extruded to form pellets. The formed polymercomposition pellet was then injection molded into testing plaques andbars. The formulation information for Examples I8 to I10 and ComparativeExample CI14 is listed in Table I10. The peak polymer recrystallizationtemperature, multi-axial impact at temperature of −30° C. andbi-directional modulus (measured on plaques), and 1% secant modulus andheat deflection temperature (measured on bars) were measured and arereported in Table I11 and I12 below.

TABLE I10 Formulation information for Samples CI4, I8, I9 and I10.Additives Calcium Examples EX5 Stearate DHT-4A CI4 None None None I81500 ppm None None I9 1500 ppm 1500 ppm None I10 1500 ppm None 500 ppm

TABLE I11 Multi-axial impact at temperature of −30° C. andbi-directional modulus of sample CI4, I8, I9 and I10. PropertyMulti-Axial Impact (2.2 m/s at −30° C.) Bi-directional Modulus Total StdMachine Std Transverse Std Energy Dev Ductility Std Direction DevDirection Dev Sample (J) (J) Index Dev (MPa) (MPa) (MPa) (MPa) CI4 28.40.6 42.5 0.7 1020 12 1142 7 I8 29.9 0.3 44.9 1.0 1137 4 1128 7 I9 29.60.4 44.9 0.7 1107 4 1130 11 I10 29.9 0.7 45.4 1.3 1143 13 1129 14

TABLE I12 1% secant modulus, heat deflection temperature, and peakpolymer recrystallization temperature of CI4, I8, I9 and I10. Property1% Secant Std Dev Heat Deflection T_(c) Sample Modulus (MPa) (MPa)temperature (° C.) (° C.) CI4 869 13 64 117.2 I8 948 10 69 119.7 I9 9165 70 119.3 I10 957 10 71 120.0

Example I11-I12

These examples demonstrate some of the physical properties exhibited bya high density polyethylene polymer that has been nucleated withnucleating agents according to the invention. Polymer compositions wereprepared by compounding (as described above) Preparation Examples EX46and EX76 into a commercially available high density polyethylene(ExxonMobil™ HDPE HD 6719) having a density of approximately 0.952 g/cm³and a melt flow index of approximately 19 dg/minute. The resin was firstground, mixed with the additives, and then compounded and extruded toform pellets. The formed polymer composition pellet was then injectionmolded into testing plaques and bars. In this example, the plaques weremolded at 15 cc/sec and the bars at 40 cc/sec, keeping the otherprocessing conditions the same as described above. The formulationinformation for Examples I11 and I12 and Comparative Example CI5 islisted in Table I13. The peak polymer recrystallization temperature,multi-axial impact at temperature of −30° C. and bi-directional modulus(measured on plaques), and 1% secant modulus, izod impact at −30° C.,and heat distortion temperature (measured on bars) were measured and arereported in Table I14 and I115 below.

TABLE I13 Formulation information for Samples CI5, I11 and I12.Additives Examples EX46 EX76 CI5 None None I11 2000 ppm None I12 None2000 ppm

TABLE I14 Multi-axial impact at temperature of −30° C. andBi-directional modulus of sample CI5, I11 and I12. Plaques molded at 15cc/sec Property Multi-Axial Impact (2.2 m/s at −30° C.) Bi-directionalModulus Total Std Machine Std Transverse Std Energy Dev Ductility StdDirection Dev Direction Dev Sample (J) (J) Index Dev (MPa) (MPa) (MPa)(MPa) CI5 30.6 0.3 45.9 0.4 879 9 952 9 I11 31.4 0.7 45.6 0.9 958 12 95713 I12 29.9 0.1 46.7 0.4 890 6 1162 4

TABLE I15 1% secant modulus, peak polymer recrystallization temperature,and heat deflection temperature of CI5, I11 and I12. Bars molded at 40cc/sec Property Heat 1% Secant Std Izod Std Deflection Modulus DevImpact Dev temperature Sample (MPa) (MPa) (J/m) (J/m) (° C.) T_(c) (°C.) CI5 854 3 30.6 6.3 67 116.8 I11 915 8 32.8 1.9 69 118.8 I12 965 133.2 1.1 71 119.0

Example I13-I15

These examples demonstrate some of the physical properties exhibited bya high density polyethylene polymer that has been nucleated withnucleating agents according to the invention. Polymer compositions wereprepared by compounding Preparation Examples EX5, EX46 and EX76 into acommercially available high density polyethylene (LyondellBasellHostalen® ACP 6541A UV) having a density of approximately 0.954 g/cm³and a melt flow index of approximately 1.5 dg/minute. The resin wasfirst ground, mixed with the additives, and then compounded and extrudedto form pellets. The formed polymer composition pellet was theninjection molded into testing plaques and bars. In this example, theplaques were molded at 220° C. and 20 cc/sec and the bars were molded at220° C. and 40 cc/sec, keeping the other processing conditions the sameas described above. The formulation information for Examples I13, I14,I15 and Comparative Example CI6 is listed in Table I16. The peak polymerrecrystallization temperature, multi-axial impact at temperature of −30°C. and bi-directional modulus (measured on plaques), and 1% secantmodulus, Izod impact, and heat deflection temperature (measured on bars)were measured and are reported in Table I17 and I18 below.

TABLE I16 Formulation information for Samples CI6, I13, I14 and I15.Additives Examples EX5 EX46 EX76 CI6 None None None I13 2000 ppm NoneNone I14 None 2000 ppm None I15 None None 2000 ppm

TABLE I17 Multi-axial impact at temperature of −30° C. andbi-directional modulus of sample CI6, I13, I14 and I15. Plaques moldedat 20 cc/sec Property Multi-Axial Impact (2.2 m/s at −30° C.)Bi-directional Modulus Total Std Machine Std Transverse Std Energy DevDuctility Std Direction Dev Direction Dev Sample (J) (J) Index Dev (MPa)(MPa) (MPa) (MPa) CI6 30.3 0.5 43.8 0.8 1016 7 1239 4 I13 29.9 0.2 43.51.0 1061 14 1305 8 I14 29.9 0.4 42.6 1.0 1057 3 1314 4 I15 28.3 0.3 44.51.0 1052 12 1198 11

TABLE I18 1% secant modulus, peak polymer recrystallization temperature,and heat deflection temperature of CI6, I13, I14 and I15. Property Heat1% Secant Std Izod Std Deflection Modulus Dev Impact Dev temperatureSample (MPa) (MPa) (J/m) (J/m) (° C.) T_(c) (° C.) CI6 923 13 46.7 1.461 117.0 I13 894 9 48.7 1.4 53 119.2 I14 858 6 47.2 1.3 54 119.0 I151061 4 36.2 1.7 80 118.5

Manufacture of Nucleated Thin Wall Injection Molded Deli-Cups

The polyethylene resins used were first ground to a 35 mesh powder. Theinventive nucleating agent was added to the resin and blended in aHenschel high intensity mixer for about 2 minutes with a blade speed ofabout 2100 rpm. The samples were then melt compounded in a MPM singlescrew extruder, with a 38 mm diameter screw. The barrel temperature ofthe extruder was ramped from 160 to 190° C. The extrudate in the form ofstrands, was cooled in a water bath and then subsequently pelletized.Deli-cups with a volumetric capacity of 16 oz. were produced in a HuskyS-90 RS40/32 injection molder, 90 ton clamp and accumulatorassisted/high speed injection unit, using a single cavity mold. Theinjection molder has a 32 mm diameter reciprocating screw, with a lengthto diameter ratio of 25:1. The barrel temperature of the extruder wasbetween 190 and 210° C. depending on the melt index of the resin, withthe hot runners temperatures also set at about 210° C. The moldtemperature was set at about 12° C. The dimensions of the Deli-cups areapproximately 117 mm diameter and 76 mm high.

Testing of Nucleated Polyethylene Deli Cups

The % haze of the parts was measured on the side wall using a BYKGardner Haze meter, according to ASTM D1023. The clarity of the partswas measured on the side wall using a BYK Gardner Haze meter. The topload of the parts was measured using a MTS Q-Test-5 instrument accordingto ASTM D 2659. The peak polymer recrystallization temperature (T_(c))for the thermoplastic polymer compositions was measured using adifferential scanning calorimeter (Mettler-Toledo DSC822 differentialscanning calorimeter). In particular, a compression molded plaque wasprepared from the pellets and a sample was taken from the plaque andheated at a rate of 20° C./minute from a temperature of 60° C. to 220°C., held at 220° C. for two minutes, and cooled at a rate ofapproximately 10° C./minute to a temperature of 60° C. The temperatureat which peak polymer crystal reformation occurred (which corresponds tothe peak polymer recrystallization temperature) was recorded for eachsample.

Example I16-I18

These examples demonstrate some of the physical properties exhibited byhigh density polyethylene polymer articles (Deli-cups) that haveproduced using a composition containing a nucleating agent according tothe invention. The polyethylene articles were prepared by compounding(as described above) Preparation Examples EX5, EX46, and EX76 into acommercially available high density polyethylene (Dowlex IP 40) having adensity of approximately 0.954 g/cm³ and a melt flow index ofapproximately 40 dg/minute. The resin was first ground, mixed with theadditives, and then compounded and extruded to form pellets as describedabove. The formed polymer composition pellet was then processed by thinwall injection molding (TWIM) to form the polyethylene articles. In thisexample, the Deli-cups were produced using a fill time of 0.21 sec. Theformulation information for Examples I116, I17, I18 and ComparativeExample CI7 is listed in Table I19. The recrystallization peak time(measured in a compression molded plaque produced with the pellets), theclarity, haze, and the top load of the deli cups were measured andreported in Table I20 below.

TABLE I19 Formulation information for Samples CI7 and I16 to I18. Allthe compositions contain 1000 ppm of Irganox1010 and 800 ppm of Irgafos168. Additives Examples EX5 EX46 EX76 CI7 0 0 0 I16 1500 ppm 0 0 I17 01500 ppm 0 I18 0 0 1500 ppm

TABLE I20 Select physical properties of Comparative Samples CI17 andsample I16 to I18. Properties Top Load Peak DSC Optical Properties LoadSample T_(c) (° C.) Haze Std Dev Clarity Std Dev (N) Std Dev CI17 114.398.2 0.11 75.1 0.89 658 10 I16 117.2 77.6 0.41 96.1 0.11 698 14 I17115.7 79.6 0.22 97.4 0.08 705 12 I18 116.5 88.1 0.08 95.7 0.09 653 9

Manufacture of Nucleated Injection Molded Food Storage Container

The polyethylene resins used were first ground to a 35 mesh powder. Theinventive nucleating agents were added to the resin and blended in aHenschel high intensity mixer for about 2 minutes with a blade speed ofabout 2100 rpm. The samples were then melt compounded in a MPM singlescrew extruder, with a 38 mm diameter screw. The barrel temperature ofthe extruder was ramped from 160 to 190° C. The extrudate in the form ofstrands, was cooled in a water bath and then subsequently pelletized.Reusable food storage containers with an approximate weight of 62 g wereproduced in a Husky S-90 RS40/32 injection molder, 90 ton clamp andaccumulator assisted/high speed injection unit, using a single cavitymold. The injection molder has a 32 mm diameter reciprocating screw,with a length to diameter ratio of 25:1. The barrel temperature of theextruder was between 190 and 220° C. depending on the melt index of theresin, with the hot runners temperatures also set at about 220° C. Themold temperature was set at about 12° C. The dimensions of the foodstorage containers are 190.5 mm×98.4 mm×76.2 mm, and the wall thicknessis about 1 mm.

Testing of Nucleated Polyethylene Food Storage Containers

The % haze of the parts was measured on the side wall using a BYKGardner Haze meter, according to ASTM D1023. The clarity of the partswas measured on the side wall using a BYK Gardner Haze meter. The topload of the parts was measured using a MTS Q-Test-5 instrument accordingto ASTM D 2659. The peak polymer recrystallization temperature (T_(c))for the thermoplastic polymer compositions was measured using adifferential scanning calorimeter (Mettler-Toledo DSC822 differentialscanning calorimeter). In particular, a compression molded plaque wasprepared from the pellets and a sample was taken from the plaque andheated at a rate of 20° C./minute from a temperature of 60° C. to 220°C., held at 220° C. for two minutes, and cooled at a rate ofapproximately 10° C./minute to a temperature of 60° C. The temperatureat which peak polymer crystal reformation occurred (which corresponds tothe peak polymer recrystallization temperature) was recorded for eachsample.

Example H1-H3

These examples demonstrate some of the physical properties exhibited bya high density polyethylene polymer article (food storage container)that has been nucleated with nucleating agents according to theinvention. The polyethylene articles were prepared by compoundingPreparation Examples EX5, EX46, and EX76 into a commercially availablehigh density polyethylene (ExxonMobil™ HDPE HD 6719) having a density ofapproximately 0.952 g/cm³ and a melt flow index of approximately 19dg/minute. The resin was first ground, mixed with the additives, andthen compounded and extruded to form pellets as described above. Theformed polymer composition pellet was then processed by injectionmolding (IM) to form the polyethylene articles. In this example, theHousewares were produced using a fill time of 2.8 sec. The formulationinformation for Examples H1, H2, H3 and Comparative Example CH1 islisted in Table TH1. The recrystallization peak time (measured in acompression molded plaque produced with the pellets), the clarity, haze,and the top load were measured and are reported in Table TH2 below.

TABLE TH1 Formulation information for Samples CH1 and H1 to H3. All thecompositions contain 1000 ppm of Irganox1010 and 800 ppm of Irgafos 168.Additives Examples EX5 EX46 EX76 CH1 0 0 0 H1 1500 ppm 0 0 H2 0 1500 ppm0 H3 0 0 1500 ppm

TABLE TH2 Select physical properties of Comparative Samples CH1 and H1to H3. Properties Top Load Peak DSC Optical Properties Load Sample T_(c)(° C.) Haze Std Dev Clarity Std Dev (N) Std Dev CH1 114.5 103.0 0.5 2.80.1 1594 26 H1 118.2 96.5 0.3 91.9 0.2 1632 29 H2 117.7 97.5 0.2 93.50.1 1691 14 H3 118.0 99.7 0.1 89.2 0.1 1690 11

Example H4-H6

These examples demonstrate some of the physical properties exhibited bya high density polyethylene polymer article (food storage container)that has been made with a resin nucleated with a nucleating agentaccording to the invention. Polyethylene articles were prepared bycompounding Preparation Examples EX5, EX46, and EX76 into a commerciallyavailable high density polyethylene (Dow™ HDPE DMDA-8965 NT 7) having adensity of approximately 0.954 g/cm³ and a melt flow index ofapproximately 66 dg/minute. The resin was first ground, mixed with theadditives, and then compounded and extruded to form pellets as describedabove. The formed polymer composition pellet was then processed byinjection molding (IM) to form the polyethylene articles. In thisexample, the housewares were produced using a fill time of 3.0 sec. Theformulation information for Examples H4, H5, H6 and Comparative ExampleCH2 is listed in Table TH3. The recrystallization peak time (measured ina compression molded plaque produced with the pellets), the clarity,haze, and the top load were measured and are reported in Table TH4below.

TABLE TH3 Formulation information for Samples CH2 and H4 to H6. All thecompositions contain 1000 ppm of Irganox1010 and 800 ppm of Irgafos 168.Additives Examples EX5 EX46 EX76 CH2 0 0 0 H4 1500 ppm 0 0 H5 0 1500 ppm0 H6 0 0 1500 ppm

TABLE TH4 Select physical properties of Comparative Samples CH2 and H4to H6. Properties Top Load Peak DSC Optical Properties Load Sample T_(c)(° C.) Haze Std Dev Clarity Std Dev (N) Std Dev CH2 113.5 103.0 0.0 2.10.3 1659 11 H4 118.5 98.4 0.1 91.2 0.3 1731 12 H5 117.3 100.0 0.0 89.90.1 1690 15 H6 118.0 101.0 0.0 83.8 0.4 1737 8

Example H7-H9

These examples demonstrate some of the physical properties exhibited bya high density polyethylene polymer article (food storage container)that has been produced using a resin nucleated with a nucleating agentaccording to the invention. Polyethylene articles were prepared bycompounding Preparation Examples EX5, EX46, and EX76 into a commerciallyavailable linear low density polyethylene (ExxonMobil™ LLDPE LL 6100.17)having a density of approximately 0.925 g/cm³ and a melt flow index ofapproximately 20 dg/minute. The resin was first ground, mixed with theadditives, and then compounded and extruded to form pellets as describedabove. The formed polymer composition pellet was then processed byinjection molding (IM) to form the polyethylene articles. In thisexample, the housewares were produced using a fill time of 2.7 sec. Theformulation information for Examples H7, H8, H9 and Comparative ExampleCH3 is listed in Table TH5. The recrystallization peak time (measured ina compression molded plaque produced with the pellets), the clarity,haze, and the top load were measured and are reported in Table TH6below.

TABLE TH5 Formulation information for Samples CH3 and H7 to H9. All thecompositions contain 1000 ppm of Irganox1010 and 800 ppm of Irgafos 168.Additives Examples EX5 EX46 EX76 CH3 0 0 0 H7 1500 ppm 0 0 H8 0 1500 ppm0 H9 0 0 1500 ppm

TABLE TH6 Select physical properties of comparative samples CH3 and H7to H9. Properties Top Load Peak DSC Optical Properties Load Sample T_(c)(° C.) Haze Std Dev Clarity Std Dev (N) Std Dev CH3 106.5 90.0 0.1 93.20.2 618 8 H7 115.3 78.0 0.1 95.2 0.1 642 8 H8 114.2 78.6 0.3 96.5 0.1650 9 H9 114.5 86.1 0.1 95.7 0.1 646 4

Example H10-H12

These examples demonstrate some of the physical properties exhibited bya high density polyethylene polymer article (food storage container)that has been made with a resin nucleated with a nucleating agentaccording to the invention. Polyethylene articles were prepared bycompounding Preparation Examples EX5, EX46, and EX76 into a commerciallyavailable linear low density polyethylene (Dowlex™ 2517) having adensity of approximately 0.919 g/cm³ and a melt flow index ofapproximately 25 dg/minute. The resin was first ground, mixed with theadditives, and then compounded and extruded to form pellets as describedabove. The formed polymer composition pellet was then processed byinjection molding (IM) to form the polyethylene articles. In thisexample, the housewares were produced using a fill time of 2.5 sec. Theformulation information for Examples H10, H11, H12 and ComparativeExample CH4 is listed in Table TH7. The recrystallization peak time(measured in a compression molded plaque produced with the pellets), theclarity, haze, and the top load were measured and are reported in TableTH8 below.

TABLE TH7 Formulation information for Sample CH4 and H10 to H12. All thecompositions contain 1000 ppm of Irganox1010 and 800 ppm of Irgafos 168.Additives Examples EX5 EX46 EX76 CH4 0 0 0 H10 1500 ppm 0 0 H11 0 1500ppm 0 H12 0 0 1500 ppm

TABLE TH8 Select physical properties of Comparative Samples CH4 and H10to H12. Properties Top Load Peak DSC Optical Properties Load SampleT_(c) (° C.) Haze Std Dev Clarity Std Dev (N) Std Dev CH4 100.3 97.0 0.184.9 0.2 426 7 H10 116.0 78.9 0.2 95.4 0.1 471 5 H11 115.0 82.0 0.1 97.80.0 464 5 H12 114.0 88.8 0.3 96.7 0.1 481 3

Formation of Nucleated Polypropylene

The different additives were added to the polypropylene base resin andblended in a Henschel high intensity mixer for about 2 minutes with ablade speed of about 2100 rpm. The samples were then melt compounded ona DeltaPlast single screw extruder, with a 25 mm diameter screw and alength to diameter ratio of 30:1. The barrel temperature of the extruderwas ramped from 190 to 230° C. and the screw speed was set at about 130rpm. The extrudate in the form of a strand, was cooled in a water bathand then subsequently pelletized.

Plaques and bars were formed through injection molding on an Arburg 40ton injection molder with a 25.4 mm diameter screw. The barreltemperature of the injection molder was 230° C. and the mold temperaturewas controlled at 25° C. The injection speed for the plaques was 2.4cc/sec, and their dimensions are about 60 mm long, 60 mm wide and 2 mmthick. These plaques were used to measure recrystallization temperature,bi-directional stiffness. The injection speed for the bars was 15cc/sec, and their dimensions are about 127 mm long, 12.7 mm wide and 3.3mm thick. These bars were used to measure 1% secant modulus, HDT andIzod impact resistance.

Testing of Nucleated Polypropylene

Flexural properties testing (reported bi-directional modulus) wasperformed on the above mentioned plaques using an MTS Q-Test-5instrument with a span of 32 mm, a fixed deflection rate of 8.53mm/minute, and a nominal sample width of 50.8 mm. Samples were preparedby cutting square sections (approximately 50 mm×50 mm) from the centersof the plaques in order to obtain an isotropically sized sample. Inaddition to testing the samples across the machine/flow direction as iscustomary (labeled as “Transverse Direction” in the results table),samples were also tested by flexing across the transverse direction toflow to measure stiffness in that direction as well (labeled as “MachineDirection” in the results table) in order to examine the bi-directionalstiffness of the plaques.

Flexural modulus testing (reported as 1% secant modulus) was performedin the above mentioned bars using a MTS Qtest/5 instrument, according toASTM D790 procedure B. Heat deflection temperature was performed in theabove mentioned bars using a Ceast HDT 3 VICAT instrument, according toASTM D648-07 method B. Izod impact testing was performed in the abovementioned bars, using a Tinius-Olsen 892T instrument, according to ASTMD256, method A. The peak polymer recrystallization temperature (T_(c))for the thermoplastic polymer compositions was measured using adifferential scanning calorimeter (Mettler-Toledo DSC822 differentialscanning calorimeter). This was accomplished by heating a roughly 5milligram sample obtained from the target plaques at 20° C./minute from50° C. to 220° C., holding at 220° C. for 2 minutes, cooling the plaquesat a rate of about 20° C./minute back to 50° C., and recording thetemperature at which peak polymer crystal reformation occurs (T_(c)).

Example P1-P6

These examples demonstrate some of the physical properties exhibited bya polypropylene polymer that has been nucleated with nucleating agentsaccording to the invention. Polymer compositions were prepared bycompounding Preparation Examples EX5, EX46, EX9, EX8, EX36 and EX76 intoa commercially available polypropylene homopolymer (LyondellBasellPro-Fax™ 6301) having a melt flow index of approximately 12 dg/minute.The resin was first mixed with the inventive nucleating agent withantioxidant and acid scavengers, then the mixture compounded andextruded to form pellets. The formed pellet was injection molded intotesting plaques and bars as described above. The formulation informationfor Examples P1 to P6 and Comparative Example CP1 is listed in Table P1.The peak polymer recrystallization temperature, bi-directional modulus,Izod impact, and heat deflection temperature were measured and reportedin Table P2 and P3 below.

TABLE P1 Formulation information for Samples CP1 and P1 to P6. All thecompositions contain 500 ppm of Irganox 1010, 1000 ppm of Irgafos 168,and 800 ppm of calcium stearate. Additives Examples EX5 EX46 EX9 EX8EX36 EX76 CP1 0 0 0 0 0 0 P1 2000 0 0 0 0 0 ppm P2 0 2000 0 0 0 0 ppm P30 0 2000 ppm 0 0 0 P4 0 0 0 2000 ppm 0 0 P5 0 0 0 0 2000 ppm 0 P6 0 0 00 0 2000 ppm

TABLE P2 Bi-directional modulus of comparative example CP1 and examplesP1 to P6 Property Bi-directional Modulus Machine Std Dev Transverse StdDev Sample Direction (MPa) (MPa) Direction (MPa) (MPa) CP1 1599 9 156211 P1 1840 21 1818 12 P2 1744 13 1759 11 P3 1709 20 1750 15 P4 1695 181771 17 P5 1745 13 1711 14 P6 1681 17 1652 12

TABLE P3 Peak polymer recrystallization temperature, Izod impact at roomtemperature, and heat deflection temperature of comparative example CP1and examples P1 to P6 Property T_(c) Izod Std Dev Heat Deflection Sample(° C.) Impact (J/m) (J/m) temperature (° C.) CP1 117.8 18.0 0.3 95 P1123.5 23.6 8.5 113 P2 122.5 33.5 6.0 110 P3 123.5 37.6 1.4 106 P4 129.432.2 4.1 111 P5 128.7 32.5 6.2 108 P6 124.4 34.3 7.3 102

Example P7-P12

These examples demonstrate some of the physical properties exhibited bya polypropylene polymer that has been nucleated with a nucleating agentaccording to the invention. Polymer compositions were prepared bycompounding Preparation Examples EX5, EX46, EX9, EX8, EX36 and EX76 intoa commercially available polypropylene homopolymer (LyondellBasellPro-Fax™ 6301) having a melt flow index of approximately 12 dg/minute.The resin was first mixed with the nucleating agents of invention withantioxidant and acid scavengers, then the mixture compounded andextruded to form pellets. The formed pellet was injection molded intotesting plaques and bars as described above. The formulation informationfor Examples P7 to P12 and Comparative Example CP2 is listed in TableP4. The peak polymer recrystallization temperature, bi-directionalmodulus, Izod impact, and heat deflection temperature were measured andreported in Table P5 and P6 below.

TABLE P4 Formulation information for Samples CP2 and P7 to P12. All thecompositions contain 500 ppm of Irganox 1010, 1000 ppm pf Irgafos 168,and 500 ppm of DHT-4A. Additives Examples EX5 EX46 EX9 EX8 EX36 EX76 CP20 0 0 0 0 0 P7 2000 0 0 0 0 0 ppm P8 0 2000 0 0 0 0 ppm P9 0 0 2000 ppm0 0 0 P10 0 0 0 2000 ppm 0 0 P11 0 0 0 0 2000 ppm 0 P12 0 0 0 0 0 2000ppm

TABLE P5 Bi-directional modulus of comparative example CP2 and examplesP7 to P12 Property Bi-directional Modulus Machine Std Dev Transverse StdDev Sample Direction (MPa) (MPa) Direction (MPa) (MPa) CP2 1540 9 154318 P7 1769 15 1733 11 P8 1776 6 1746 7 P9 1719 12 1762 8 P10 1691 9 166011 P11 1697 14 1638 7 P12 1691 9 1660 11

TABLE P6 Peak polymer recrystallization temperature, Izod impact at roomtemperature, and heat deflection temperature of comparative example CP2and examples P7 to P12 Property T_(c) Izod Std Dev Heat DeflectionSample (° C.) Impact (J/m) (J/m) temperature (° C.) CP2 116.6 22.6 5.693 P7 126.3 32.4 6.3 111 P8 126.4 30.1 5.8 111 P9 129.5 30.2 6.9 109 P10127.2 31.2 7.0 108 P11 127.7 31.7 5.3 108 P12 127.2 31.2 7.0 108

Example P13-P18

These examples demonstrate some of the physical properties exhibited bya polypropylene polymer that has been nucleated with a nucleating agentaccording to the invention. Polymer compositions were prepared bycompounding Preparation Examples EX5, EX46, EX9, EX8, EX36 and EX76 intoa commercially available impact polypropylene copolymer (LyondellBasellPro-fax™ SD375S) having a melt flow index of approximately 18 dg/minute.

The resin was first mixed with the nucleating agents of invention withantioxidant and acid scavengers, then the mixture compounded andextruded to form pellets. The formed pellet was injection molded intotesting plaques and bars as described above. The formulation informationfor Examples P13 to P18 and Comparative Example CP3 is listed in TableP7. The peak polymer recrystallization temperature, bi-directionalmodulus, Izod impact, and heat deflection temperature were measured andreported in Table P8 and P9 below.

TABLE P7 Formulation information for Samples CP3 and P13 to P18. All thecompositions contain 500 ppm of Irganox 1010, 1000 ppm of Irgafos 168,and 800 ppm of calcium stearate. Additives Examples EX5 EX46 EX9 EX8EX36 EX76 CP3 0 0 0 0 0 0 P13 2000 0 0 0 0 0 ppm P14 0 2000 0 0 0 0 ppmP15 0 0 2000 ppm 0 0 0 P16 0 0 0 2000 ppm 0 0 P17 0 0 0 0 2000 ppm 0 P180 0 0 0 0 2000 ppm

TABLE P8 Bi-directional modulus of comparative example CP3 and examplesP13 to P18 Property Bi-directional Modulus Machine Std Dev TransverseStd Dev Sample Direction (MPa) (MPa) Direction (MPa) (MPa) CP3 1168 121090 4 P13 1314 8 1262 13 P14 1320 13 1228 12 P15 1300 12 1277 4 P161272 7 1249 3 P17 1280 9 1220 14 P18 1294 15 1229 12

TABLE P9 Peak polymer recrystallization temperature, and heat deflectiontemperature of comparative example CP3 and examples P13 to P18 PropertyT_(c) Izod Std Dev Heat Deflection Sample (° C.) Impact (J/m) (J/m)temperature (° C.) CP3 117.0 107.2 9.8 76 P13 125.9 83.4 11.2 97 P14124.6 94.4 10 96 P15 125.2 87.4 11.7 94 P16 130.5 87.2 8.3 98 P17 128.783.4 10.3 96 P18 128.3 89.8 9.2 96

Example P19-P24

These examples demonstrate some of the physical properties exhibited bya polypropylene polymer that has been nucleated with a nucleating agentaccording to the invention. Polymer compositions were prepared bycompounding Preparation Examples EX5, EX46, EX9, EX8, EX36 and EX76 intoa commercially available impact polypropylene copolymer (LyondellBasellPro-fax™ SD375S) having a melt flow index of approximately 18 dg/minute.

The resin was first mixed with the nucleating agents of invention withantioxidant and acid scavengers, then the mixture compounded andextruded to form pellets. The formed pellet was injection molded intotesting plaques and bars as described above. The formulation informationfor Examples P19 to P24 and Comparative Example CP4 is listed in TableP10. The peak polymer recrystallization temperature, bi-directionalmodulus, Izod impact, and heat deflection temperature were measured andreported in Table P11 and P12 below.

TABLE P10 Formulation information for Samples CP4 and P19 to P24. Allthe compositions contain 500 ppm of Irganox 1010, 1000 ppm of Irgafos168, and 500 ppm of DHT-4A. Additives Examples EX5 EX46 EX9 EX8 EX36EX76 CP4 0 0 0 0 0 0 P19 2000 0 0 0 0 0 ppm P20 0 2000 0 0 0 0 ppm P21 00 2000 ppm 0 0 0 P22 0 0 0 2000 ppm 0 0 P23 0 0 0 0 2000 ppm 0 P24 0 0 00 0 2000 ppm

TABLE P11 Bi-directional modulus of comparative example CP4 and examplesP19 to P24 Property Bi-directional Modulus Machine Std Dev TransverseStd Dev Sample Direction (MPa) (MPa) Direction (MPa) (MPa) CP4 1205 121155 11 P19 1353 4 1298 4 P20 1343 11 1280 9 P21 1340 9 1297 6 P22 134919 1300 15 P23 1311 10 1271 18 P24 1335 8 1217 9

TABLE P12 Peak polymer recrystallization temperature, and heatdeflection temperature of comparative example CP4 and examples P19 toP24 Property T_(c) Izod Std Dev Heat Deflection Sample (° C.) Impact(J/m) (J/m) temperature (° C.) CP4 120.8 99.6 5.3 83 P19 128.9 82.5 7.6101 P20 128.1 90.8 11.3 100 P21 128.7 92.3 6.1 96 P22 132.7 83.5 4.9 99P23 132.8 84.8 5.7 100 P24 131.3 84.9 12.1 98

Manufacture of Nucleated Polyethylene by Injection Molding

In the following injection molding examples, the polyethylene resinswere prepared as described above in connection with the precedinginjection molding examples. Plaques and bars were formed throughinjection molding on an Arburg 40 ton injection molder with a 25.4 mmdiameter screw. The barrel temperature of the injection molder wasbetween 190 and 230° C. depending on the melt index of the resin and themold temperature was controlled at 25° C.

Unless otherwise specified, the injection speed for the plaques was 15cc/sec, and their dimensions were about 60 mm long, 60 mm wide and 2 mmthick. These plaques were used to measure bi-directional shrinkage,recrystallization temperature, and bi-directional stiffness.

Unless otherwise specified, the injection speed for the bars was 40cc/sec, and their dimensions were about 127 mm long, 12.7 mm wide and3.3 mm thick. These bars were used to measure 1% secant modulus and HDT.

Testing of Nucleated Polyethylene

Shrinkage is measured in the plaques, in both the machine direction (MD)and the transverse direction (TD), after 48 hours aging at ambientconditions according to ASTM D955. The percent shrinkage for eachdirection is calculated using the following equation:

$\left( \frac{\left( {{{Mold}\mspace{14mu} {Dimension}} - {{Test}\mspace{14mu} {Specimen}\mspace{14mu} {Dimension}}} \right)}{{Mold}\mspace{14mu} {Dimension}} \right) \times 100\%$

Flexural properties testing (reported as bi-directional modulus) wasperformed on the above mentioned plaques using an MTS Q-Test-5instrument with a span of 32 mm, a fixed deflection rate of 8.53mm/minute, and a nominal sample width of 50.8 mm. Samples were preparedby cutting square sections (approximately 50 mm×50 mm) from the centersof the plaques in order to obtain an isotropically sized sample. Inaddition to testing the samples across the machine/flow direction as iscustomary (labeled as “Transverse Direction” in the results table),samples were also tested by flexing across the direction perpendicularto the flow direction to measure stiffness in that direction (labeled as“Machine Direction” in the results table) in order to examine thebi-directional stiffness of the plaques.

The peak polymer recrystallization temperature (T_(c)) for thethermoplastic polymer compositions was measured using a differentialscanning calorimeter (Mettler-Toledo DSC822 differential scanningcalorimeter). In particular, a sample was taken from the target part andheated at a rate of 20° C./minute from a temperature of 60° C. to 220°C., held at 220° C. for two minutes, and cooled at a rate ofapproximately 10° C./minute to a temperature of 60° C. The temperatureat which peak polymer crystal reformation occurred (which corresponds tothe peak polymer recrystallization temperature) was recorded for eachsample.

Examples Q1-Q12

These examples demonstrate some of the physical properties exhibited bya high density polyethylene polymer that has been nucleated with a blendof EX76 and an acid scavenger, specifically zinc stearate (ZnSt) or asynthetic dihydrotalcite compound (DHT-4A). Polymer compositions wereprepared by compounding (as described above) Preparation Example EX76and different acid scavengers into a commercially available high densitypolyethylene (Nova Sclair® 19G) having a density of approximately 0.960g/cm³ and a melt flow index of approximately 1.2 dg/minute. The resinwas first ground, mixed with the additives, and then compounded andextruded to form pellets. The formed polymer composition pellet was theninjection molded into testing plaques and bars.

The formulation information for Examples Q1 to Q12 and ComparativeExample CQ1 is listed in table Q1. The peak polymer recrystallizationtemperature (T_(c)), bi-directional modulus (measured on plaques), and1% secant modulus and heat deflection temperature (measured on bars) arereported in Tables Q2 and Q3 below.

TABLE Q1 Formulation information for Samples CQ1 and Q1 to Q12.Additives Examples EX76 DHT-4A ZnSt CQ1 None None None Q1  500 ppm NoneNone Q2  375 ppm 125 ppm None Q3  375 ppm None 125 ppm Q4 1000 ppm NoneNone Q5  750 ppm 250 ppm None Q6  750 ppm None 250 ppm Q7 1500 ppm NoneNone Q8 1125 ppm 375 ppm None Q9 1125 ppm None 375 ppm Q10 2000 ppm NoneNone Q11 1500 ppm 500 ppm None Q12 1500 ppm None 500 ppm

TABLE Q2 Bi-directional modulus and bi-directional shrinkage of samplesCQ1 and Q1 to Q12. Property Bi-directional Bi-directional ModulusShrinkage Machine Std Transverse Std Machine Transverse Sam- DirectionDev Direction Dev Direction Direction ple (MPa) (MPa) (MPa) (MPa) (MPa)(MPa) CQ1 1085 14 1282 29 2.17 1.54 Q1 1016 6 1353 3 1.28 0.81 Q2 1042 81343 6 1.2 0.93 Q3 1197 12 1394 8 0.83 1.27 Q4 1057 3 1336 3 1.07 0.92Q5 1081 7 1354 10 1.09 0.99 Q6 1247 14 1313 7 0.65 1.48 Q7 1067 4 1329 91.05 0.96 Q8 1108 14 1334 7 1.03 1.06 Q9 1271 5 1278 5 0.6 1.54 Q10 108611 1322 12 1.02 1.01 Q11 1118 15 1336 7 0.95 1.16 Q12 1298 11 1292 30.54 1.55

EX76 without ZnSt or DHT-4A imparts some machine direction (MD) crystalgrowth orientation as evidenced by the decrease in MD shrinkage. WhenDHT-4A is used as the acid scavenger at a 3:1 ratio of EX76 to DHT-4A, astronger MD orientation (lower MD than TD shrinkage) is present atloadings of 1,500 ppm of the blend. When ZnSt is used as the acidscavenger, the strong MD orientation is apparent at loadings of theblend as low as 500 ppm. This is evident from the lower MD shrinkage,the higher MD stiffness, and a decrease in the TD stiffness.

TABLE Q3 1% secant modulus, heat deflection temperature, and peakpolymer recrystallization temperature of CQ1 and Q1 to Q12. Property 1%Secant Std Dev Heat Deflection T_(c) Sample Modulus (MPa) (MPa)temperature (° C.) (° C.) CQ1 982.4 0.9 59.70 117.17 Q1 1121.7 1.2 67.80119.17 Q2 1133.6 1.1 69.00 119.00 Q3 1221.9 2.1 78.30 118.67 Q4 1155.31.9 68.10 118.83 Q5 1162.2 3.1 70.50 119.00 Q6 1312.2 0.7 85.70 119.00Q7 1182.4 3.4 71.90 119.00 Q8 1189.1 0.4 75.10 119.17 Q9 1376.3 1.191.00 119.00 Q10 1203.8 0.7 74.50 119.33 Q11 1214.2 1.1 75.30 119.33 Q121416.4 3 93.40 118.83

As can be seen from Table Q3, the blends of EX76 with an acid scavengerhad the same effect on the T_(c) as EX76 alone. The stiffnessmeasurements and HDT in flex bars confirmed that using EX76 togetherwith ZnSt or DHT-4A significantly improves the performance of EX76 ascompared to EX76 alone. When a blend of the nucleating agent and acidscavenger are used, lower loadings of the nucleating agent (EX76) areable to impart similar or better properties than higher loadings of EX76alone.

Examples R1-R9

These examples demonstrate some of the physical properties exhibited bya high density polyethylene polymer that has been nucleated with blendsof EX76 and ZnSt at different ratios. Polymer compositions were preparedby compounding (as described above) Preparation Example EX76 and ZnStinto a commercially available high density polyethylene (Nova Sclair®19G) having a density of approximately 0.960 g/cm³ and a melt flow indexof approximately 1.2 dg/minute. The resin was first ground, mixed withthe additives, and then compounded and extruded to form pellets. Theformed polymer composition pellet was then injection molded into testingplaques and bars.

The formulation information for Examples R1 to R9 and ComparativeExamples CR1 and CR2 are listed in table R1. The peak polymerrecrystallization temperature (T_(c)), bi-directional modulus (measuredon plaques), and 1% secant modulus and heat deflection temperature(measured on bars) are reported in Tables R2 and R3 below.

TABLE R1 Formulation information for Samples CR1, CR2, and R1 to R9.Additives Examples EX76 ZnSt CR1 None None CR2 None 1000 ppm  R1 1000ppm  None R2 2000 ppm  None R3 875 ppm 125 ppm R4 750 ppm 250 ppm R5 667ppm 333 ppm R6 500 ppm 500 ppm R7 333 ppm 667 ppm R8 250 ppm 750 ppm R9125 ppm 875 ppm

TABLE R2 Bi-directional modulus and bi-directional shrinkage of samplesCR1, CR2, and R1 to R9. Property Bi-directional Bi-directional ModulusShrinkage Machine Std Transverse Std Machine Transverse Sam- DirectionDev Direction Dev Direction Direction ple (MPa) (MPa) (MPa) (MPa) (MPa)(MPa) CR1 1168 7.6 1382 8.4 2.11 1.33 CR2 1164 9.3 1375 4 2.13 1.32 R11140 6.6 1525 8.7 1.14 0.57 R2 1201 8.2 1483 1.9 0.95 0.65 R3 1297 4.81338 6.4 0.59 1.05 R4 1301 6.1 1294 7.5 0.51 1.16 R5 1286 5.6 1253 2.60.49 1.22 R6 1287 6.7 1289 9.1 0.57 1.24 R7 1237 1.6 1284 8.2 0.72 1.18R8 1221 8.4 1309 11.8 0.79 1.12 R9 1214 3.6 1342 6.8 1.01 1.07

The data for Sample CR2 show that the addition of ZnSt alone does nothave a significant effect on the bi-directional stiffness or theshrinkage of this resin. This is evidence that the ZnSt does notnucleate the resin. Samples R1 and R2 show that EX76 without ZnStimparts MD crystal growth orientation (decreasing the MD shrinkagecompared to CR1 and CR2). When ZnSt is used together with EX76, a muchstronger MD orientation (very low MD shrinkage) is observed. This istrue even with a 1:4 ratio blend, where EX76 is only present at 125 ppmin the resin.

When EX76 and ZnSt are used together, a very high MD stiffness and adecrease in the TD stiffness are observed, which is indicative of a verystrong MD orientation. The MD stiffness imparted by all of the blends ishigher than the MD stiffness of EX76 alone at both 1,000 ppm and 2,000ppm. This is surprising since the resins compounded with the blendscontain less EX76. The highest MD stiffness is obtained with blends ofEX76 and ZnSt having ratios ranging from 4:1, 3:1, 2:1 and 1:1. But evenat ratios of 1:3 and 1:4 (which refer to EX76 loadings of 250 ppm and125 ppm, with ZnSt at 750 ppm and 875 ppm respectively), MD stiffness issimilar or slightly higher than EX76 alone at 2,000 ppm.

TABLE R3 1% secant modulus, heat deflection temperature, and peakpolymer recrystallization temperature of CR1, CR2, and R1 to R9.Property 1% Secant Std Dev Heat Deflection T_(c) Sample Modulus (MPa)(MPa) temperature (° C.) (° C.) CR1 889 21.9 62.20 116.33 CR2 882 761.70 116.33 R1 1070 6.2 67.40 118.50 R2 1073 5.6 74.10 118.17 R3 11646.3 84.50 118.17 R4 1182 9.1 86.90 118.17 R5 1195 4.2 85.00 118.00 R61173 8 86.20 118.33 R7 1115 6.5 81.60 118.17 R8 1077 15.6 77.30 117.83R9 1049 9.9 74.20 117.67

As can be seen from the data in Table R3, EX76 increased the T_(c) ofthe resin. The different blends of EX76 with ZnSt did not improve theT_(c) over that observed with EX76 alone. Indeed, the T_(c) decreasedslightly as the amount of EX76 decreased.

The stiffness measurements and HDT in flex bars confirmed the synergybetween EX76 and ZnSt. The blends having ratios of 4:1, 3:1, 2:1, 1:1and 1:2 (EX76:ZnSt) imparted much higher stiffness and HDT than EX76alone. And the blends of EX76 with ZnSt at ratios of 1:3 and 1:4imparted stiffness and HDT values similar to those of EX76 alone. Thismeans that one could use a resin containing a blend of EX76 at 125 ppmand ZnSt at 875 ppm and still obtain similar performance to a resincontaining EX76 alone at 2,000 ppm.

Examples S1-S5

These examples demonstrate some of the physical properties exhibited bya high density polyethylene polymer that has been nucleated with blendsof EX76 and ZnSt at different ratios. Polymer compositions were preparedby compounding (as described above) Preparation Example EX76 anddifferent acid scavengers into a commercially available high densitypolyethylene (Dow HDPE DMDA-8007 NT7) having a density of approximately0.967 g/cm³ and a melt flow index of approximately 8.3 dg/minute. Theresin was first ground, mixed with the additives, and then compoundedand extruded to form pellets. The formed polymer composition pellet wasthen injection molded into testing plaques and bars.

The formulation information for Examples S1 to S5 and ComparativeExample CS1 and CS2 are listed in table S1. The peak polymerrecrystallization temperature (T_(c)), bi-directional modulus (measuredon plaques), and 1% secant modulus and heat deflection temperature(measured on bars) are reported in Tables S2 and S3 below.

TABLE S1 Formulation information for Samples CS1, CS2, and S1 to S5.Additives Examples EX76 ZnSt CS1 None None CS2 None 1000 ppm  S1 1000ppm  None S2 2000 ppm  None S3 875 ppm 125 ppm S4 750 ppm 250 ppm S5 667ppm 333 ppm

TABLE S2 Bi-directional modulus and bi-directional shrinkage of samplesCS1, CS2, and S1 to S5. Property Bi-directional Bi-directional ModulusShrinkage Machine Std Transverse Std Machine Transverse Sam- DirectionDev Direction Dev Direction Direction ple (MPa) (MPa) (MPa) (MPa) (MPa)(MPa) CS1 1146 10.8 1233 19.0 1.96 1.75 CS2 1114 12.6 1212 10.2 1.981.74 S1 1127 18.4 1302 15.6 0.90 0.90 S2 1194 7.0 1340 5.2 0.87 0.94 S31301 15.1 1234 19.1 0.58 1.23 S4 1286 16.5 1187 18.0 0.57 1.25 S5 123811.5 1192 8.9 0.57 1.26

The data for Sample CS2 show that the addition of ZnSt alone does nothave a significant effect on the bi-directional stiffness or theshrinkage of this resin. These observations confirm that the ZnSt doesnot nucleate the resin. The data for Samples S1 and S2 show that EX76alone imparts MD crystal growth orientation (decreasing the MD shrinkagecompared to CS1 and CS2). When ZnSt and EX76 are used together, a muchstronger MD orientation (very low MD shrinkage) is observed. This istrue for all of the blend ratios tested.

When a blend of EX76 and ZnSt is used, a very high MD stiffness and adecrease in the TD stiffness are observed, which is indicative of a verystrong MD orientation. The MD stiffness imparted by any of the blends ata total loading of 1,000 ppm is higher than that imparted by EX76 alone,even at a loading of 2,000 ppm. These results are consistent with thoseobserved with lower melt flow index polyethylene resins.

TABLE S3 1% secant modulus, heat deflection temperature, and peakpolymer recrystallization temperature of CS1, CS2, and S1 to S5.Property 1% Secant Std Dev Heat Deflection T_(c) Sample Modulus (MPa)(MPa) temperature (° C.) (° C.) CS1 958 5.2 66.50 116.67 CS2 940 3.864.60 117.67 S1 1137 7.8 77.60 120.33 S2 1227 14.2 82.00 120.67 S3 132815.3 90.10 120.17 S4 1322 6.1 89.00 120.00 S5 1288 4.6 88.40 120.50

As can be seen from the data in Table S3, EX76 increased the T_(c) ofthe resin. The different blends of EX76 with ZnSt did not improve theT_(c) over that observed with EX76 alone. In fact, the T_(c) slightlydecreased as the amount of EX76 decreased.

The stiffness measurements and HDT in flex bars confirmed the synergybetween EX76 and ZnSt. The blends at ratios of 3:1, 2:1 and 1:1(EX76:ZnSt) imparted much higher stiffness and HDT values than EX76alone.

Examples T1-T5

These examples demonstrate some of the physical properties exhibited bya high density polyethylene polymer that has been nucleated with blendsof EX76 and ZnSt at different ratios. Polymer compositions were preparedby compounding (as described above) Preparation Example EX76 anddifferent acid scavengers into a commercially available high densitypolyethylene (Dowlex™ IP40) having a density of approximately 0.952g/cm³ and a melt flow index of approximately 40 dg/minute. The resin wasfirst ground, mixed with the additives, and then compounded and extrudedto form pellets. The formed polymer composition pellet was theninjection molded into testing plaques and bars.

The formulation information for Examples T1 to T5 and ComparativeExample CT1 and CT2 are listed in table T1. The peak polymerrecrystallization temperature (T_(c)), bi-directional modulus (measuredon plaques), and 1% secant modulus and heat deflection temperature(measured on bars) are reported in Tables T2 and T3 below.

TABLE T1 Formulation information for Samples CT1, CT2, and T1 to T5.Additives Examples EX76 ZnSt CT1 None None CT2 None 1000 ppm  T1 1000ppm  None T2 2000 ppm  None T3 875 ppm 125 ppm T4 750 ppm 250 ppm T5 667ppm 333 ppm

TABLE T2 Bi-directional modulus and bi-directional shrinkage of samplesCT1, CT2, and T1 to T5. Property Bi-directional Bi-directional ModulusShrinkage Machine Std Transverse Std Machine Transverse Sam- DirectionDev Direction Dev Direction Direction ple (MPa) (MPa) (MPa) (MPa) (MPa)(MPa) CT1 896 4.2 921 5.3 1.78 1.63 CT2 910 4.9 931 5.5 1.79 1.64 T1 9261.3 985 3.1 1.41 1.28 T2 946 1.0 970 2.8 0.95 1.00 T3 967 3.3 959 4.01.10 1.29 T4 1006 0.5 934 0.6 0.91 1.39 T5 1044 3.7 906 2.5 0.81 1.46

The data for Sample CT2 shows that the addition of ZnSt alone does nothave a significant effect on the bi-directional stiffness or theshrinkage of this resin. This is evidence that the ZnSt does notnucleate the resin. Samples T1 and T2 show that EX76 alone imparts MDcrystal growth orientation (decreasing the MD shrinkage compared to CT1and CT2). When both ZnSt and EX76 are used together, a much stronger MDorientation (very low MD shrinkage) is present. This is true for all ofthe different blend ratios tested.

When EX76 and ZnSt are used together, a very high MD stiffness and adecrease in the TD stiffness are observed, which is indicative of a verystrong MD orientation. The MD stiffness imparted by all of the blends ishigher than the MD stiffness of EX76 alone at loadings of 1,000 and2,000 ppm. These results are consistent with those observed with otherHDPE resins.

TABLE T3 1% secant modulus, heat deflection temperature, and peakpolymer recrystallization temperature (T_(c)) of CT1, CT2, and T1 to T5.Property 1% Secant Std Dev Heat Deflection T_(c) Sample Modulus (MPa)(MPa) temperature (° C.) (° C.) CT1 753 9.6 62.30 114.83 CT2 768 9.262.10 114.67 T1 845 9 66.40 116.17 T2 943 1.5 74.30 116.67 T3 892 6.673.10 116.50 T4 961 8.7 79.30 115.83 T5 996 10 80.70 115.67

As can be seen from the data in Table T3, EX76 increased the T_(c) ofthe resin. The different blends of EX76 with ZnSt did not improve theT_(c) over that observed with EX76 alone.

The stiffness measurement and HDT in flex bars confirm the synergybetween EX76 and ZnSt. The blends having ratios of 3:1, 2:1 and 1:1imparted much higher stiffness and HDT values than EX76 alone.

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the subject matter of this application (especiallyin the context of the following claims) are to be construed to coverboth the singular and the plural, unless otherwise indicated herein orclearly contradicted by context. The terms “comprising,” “having,”“including,” and “containing” are to be construed as open-ended terms(i.e., meaning “including, but not limited to,”) unless otherwise noted.Recitation of ranges of values herein are merely intended to serve as ashorthand method of referring individually to each separate valuefalling within the range, unless otherwise indicated herein, and eachseparate value is incorporated into the specification as if it wereindividually recited herein. All methods described herein can beperformed in any suitable order unless otherwise indicated herein orotherwise clearly contradicted by context. The use of any and allexamples, or exemplary language (e.g., “such as”) provided herein, isintended merely to better illuminate the subject matter of theapplication and does not pose a limitation on the scope of the subjectmatter unless otherwise claimed. No language in the specification shouldbe construed as indicating any non-claimed element as essential to thepractice of the subject matter described herein.

Preferred embodiments of the subject matter of this application aredescribed herein, including the best mode known to the inventors forcarrying out the claimed subject matter. Variations of those preferredembodiments may become apparent to those of ordinary skill in the artupon reading the foregoing description. The inventors expect skilledartisans to employ such variations as appropriate, and the inventorsintend for the subject matter described herein to be practiced otherwisethan as specifically described herein. Accordingly, this disclosureincludes all modifications and equivalents of the subject matter recitedin the claims appended hereto as permitted by applicable law. Moreover,any combination of the above-described elements in all possiblevariations thereof is encompassed by the present disclosure unlessotherwise indicated herein or otherwise clearly contradicted by context.

What is claimed is:
 1. A compound conforming to the structure of Formula (CX)

wherein R₁₁₁ is selected from the group consisting of a cyclopentyl group and moieties conforming to the structure of Formula (CXI); R₁₁₂ is selected from the group consisting of hydrogen and hydroxy; Formula (CXI) is

R₁₁₅ is selected from the group consisting of hydrogen, a halogen, methoxy, and phenyl; x is a positive integer; each M₁ is a metal cation; y is the valence of the cation; z is a positive integer; b is zero or a positive integer; when b is a positive integer, each Q₁ is a negatively-charged counterion and a is the valence of the negatively-charged counterion; and the values of x, y, z, a, and b satisfy the equation x+(ab)=yz; provided if R₁₁₅ is hydrogen, then R₁₁₂ is hydrogen, x is 1, M₁ is a lithium cation, y is 1, z is 1, and b is zero; and provided if R₁₁₅ is a methoxy group, then R₁₁₂ is a hydroxy group.
 2. The compound of claim 1, wherein M₁ is a cation of a metal selected from the group consisting of alkali metals and alkaline earth metals.
 3. The compound of claim 2, wherein M₁ is a cation of a metal selected from the group consisting of alkali metals.
 4. The compound of claim 3, wherein M₁ is a lithium cation.
 5. The compound of claim 1, wherein R₁₁₁ is a cyclopentyl group.
 6. The compound of claim 5, wherein x is 1, M₁ is a lithium cation, y is 1, z is 1, and b is zero.
 7. The compound of claim 1, wherein R₁₁₁ is a moiety conforming to the structure of Formula (CXI).
 8. The compound of claim 7, wherein R₁₁₅ is hydrogen.
 9. The compound of claim 7, wherein R₁₁₅ is a methoxy group.
 10. The compound of claim 9, wherein x is 1, M₁ is a lithium cation, y is 1, z is 1, and b is zero.
 11. The compound of claim 7, wherein R₁₁₅ is a halogen.
 12. The compound of claim 11, wherein R₁₁₅ is chlorine.
 13. The compound of claim 12, wherein R₁₁₂ is hydrogen.
 14. The compound of claim 13, wherein x is 1, M₁ is a sodium cation, y is 1, z is 1, and b is zero.
 15. A composition comprising a polyolefin polymer and the compound of claim
 1. 16. A composition comprising a polyolefin polymer and the compound of claim
 4. 17. A composition comprising a polyolefin polymer and the compound of claim
 5. 18. A composition comprising a polyolefin polymer and the compound of claim
 6. 19. A composition comprising a polyolefin polymer and the compound of claim
 8. 20. A composition comprising a polyolefin polymer and the compound of claim
 9. 21. A composition comprising a polyolefin polymer and the compound of claim
 10. 22. A composition comprising a polyolefin polymer and the compound of claim
 11. 23. A composition comprising a polyolefin polymer and the compound of claim
 12. 24. A composition comprising a polyolefin polymer and the compound of claim
 13. 25. A composition comprising a polyolefin polymer and the compound of claim
 14. 26. An additive composition comprising the compound of claim 1 and an acid scavenger selected from the group consisting of synthetic hydrotalcite compounds and metal salts of C₁₂-C₂₂ fatty acids.
 27. The additive composition of claim 26, wherein the acid scavenger is selected from the group consisting of the zinc, potassium, and lanthanum salts of stearic acid.
 28. The additive composition of claim 26, wherein the nucleating agent and the acid scavenger are present in the composition in a ratio of about 4:1 to about 1:4 based on the weight of the nucleating agent and the acid scavenger in the additive composition.
 29. The additive composition of claim 27, wherein the nucleating agent and the acid scavenger are present in the composition in a ratio of about 4:1 to about 1:4 based on the weight of the nucleating agent and the acid scavenger in the additive composition. 